CN1498931A - Aqueous dispersion for chemical mechanical polishing and its use - Google Patents

Abstract

Provided are an aqueous dispersion for chemical mechanical polishing, which planarizes a surface to be polished and has high shelf stability, a chemical mechanical polishing process excellent in selectivity when surfaces of different materials are polished, and a production process of a semiconductor device. A first aqueous dispersion contains a water-soluble quaternary ammonium salt, an inorganic acid salt, abrasive grains and an aqueous medium. A second aqueous dispersion contains at least a water-soluble quaternary ammonium salt, another basic organic compound than the water-soluble quaternary ammonium salt, an inorganic acid salt, a water-soluble polymer, abrasive grains and an aqueous medium. The second aqueous dispersion is composed of a first aqueous dispersion material (I) obtained by mixing a water-soluble quaternary ammonium salt and an inorganic acid salt into an aqueous medium, and a second aqueous dispersion material (II) obtained by mixing a water-soluble polymer and another basic organic compound than the water-soluble quaternary ammonium salt into an aqueous medium. Abrasive grains are contained in at least one of the aqueous dispersion materials.

Description

The water dispersion and the purposes that are used for chemically machinery polished

Background of the present invention

The field of the invention:

The present invention relates to a kind of CMP (Chemical Mechanical Polishing) process that is used for the water dispersion of chemically machinery polished and utilizes this dispersion.In addition, the invention particularly relates to a kind of high storage stability that has, even go bad along with the time when preventing under the high density state to store, can provide glazed surface with excellent complanation and minimizing surface imperfection and the water dispersion that is used for chemically machinery polished that can be used for producing semiconductor devices by chemically machinery polished, utilize the excellent polishing of having of this dispersion and remove the optionally production technique of CMP (Chemical Mechanical Polishing) process and semiconductor devices.

Background technology:

The increase of the formation in semiconductor devices along with integrated level and multilayer wiring adopts a kind of chemically machinery polished to be used for polishing film to be processed.This technology is by being embedded in the groove with required pattern with suitable wiring material, in hole or the analogue (forming on the dielectric medium of process wafer) and subsequently chemistry and mechanical polishing dielectric medium and be used to remove excessive wiring material and form and connect up.

Except forming wiring, this CMP (Chemical Mechanical Polishing) process also is used to form electrical condenser, and gate electrode and analogue and employing are in the mirror polish of silicon wafer such as SOI (silicon on isolator) base material.

Object by this CMP (Chemical Mechanical Polishing) process polishing comprises various films such as polysilicon film (aggregate pipeline silicon fiml), monocrystalline silicon membrane, silicon oxide film, aluminium film, tungsten film and copper film.

In this chemical-mechanical polishing step, if removing speed V (dust/minute) polishing down by wiring material being embedded in the initial excessive film with thickness X (dust) that forms in groove or the analogue, object should obtain naturally by only carrying out polish standard time X/V (min) so.But in the production stage of the reality of semiconductor devices, the polishing of crossing of the time X/V (min) that is above standard is stayed wiring material on the other parts except that groove or analogue with removal." recessed curved " (part wiring becomes the concave surface form) or " erosions " (becoming the concave surface form by alternately forming the alternately part of wiring that wiring portion and insulated part form) are crossed polishing by these and are caused.These phenomenons are not preferred, because semiconductor devices output descends.

In addition, the surface comprises that the defective of so-called " scratch " of wearing and tearing shape state can cause by polishing in some cases.This phenomenon also can bend and corrode and the output of reduction semiconductor devices in some cases as recessed.

Various compositions have been proposed as being used to suppress these the recessed water dispersion that is used for chemically machinery polished with erosive, water dispersions that is used for chemically machinery polished that is used to suppress the water dispersion that is used for chemically machinery polished of surface imperfection such as scratch and has these two kinds of performances simultaneously bent.

For example open, excellent surface planarization ability can realize (Japanese patent application postpones open No.154760/1993) by the polishing composition silicon wafer that use comprises silica and piperazine.But the basal component piperazine in the disclosure composition is a kind of target substance of the discharging that controls environment, so its use brings problem in safety with aspect environmental influence.

In addition, disclose and comprised at least a silicon-dioxide that is selected from, aluminum oxide, cerium oxide, titanium oxide, silicon nitride, the abrasive grain of zirconium white and Manganse Dioxide and water and comprise the composition that is used to polish of solubilised state alkaline organic compound in addition.Allegedly utilize these compositions that are used to polish can realize big removal speed, and can reduce the appearance of surface imperfection on glazed surface (referring to, for example, Japanese patent application postpones open No.321569/1998).

Along with the microminiaturization that requires to increase integrated level and semiconductor devices, developed microminiaturized and thin dielectric formation of cloth string pitch.By the microminiaturization to the cloth string pitch, silicon oxide film and the barrier layer of being made up of nitride such as silicon nitride or titanium nitride also become tiny.If but barrier layer is crossed polishing, the expectation function of barrier layer be can not realize, and erosion or similar phenomenon caused, can damage function so in some cases as semiconductor substrate.

In addition, the feasible deposition of the surface imperfection influence dielectric electrical property variation thereon that comprises scratch on the glazed surface, and this influence becomes bigger by forming thin dielectric medium.

Use the above-mentioned this composition that is used to polish to polish if having the polished surface of wanting of above-mentioned barrier layer, be not easy to improve simultaneously polishing and removal selectivity, and reduce the surface imperfection that comprises scratch at layer that will polish and barrier layer.

" polishing and removal selectivity " used herein is meant the polishing and the removal of a kind of material realization two-forty that will polish, polishing of other material simultaneously and the low performance of removal speed, with be meant when polishing by for example, when the institute that at least 2 materials are formed wanted polished surface, only a kind of material that will polish can high-level efficiency polishes and the performance that do not have to polish other material that will polish.More specifically, term " at the layer and the polishing of barrier layer that will polish and remove selectivity " be meant layer can high-level efficiency polishing and the performance that do not have to polish barrier layer of when polishing the layer that all will polish and barrier layer simultaneously, only will polishing.

In order to address the above problem, proposed at the polishing of polysilicon film and silicon oxide film with remove aspect the selectivity improved composition and at the composition that is controlled aspect the removal speed (following also be called " polishing speed ") of polishing nitride.

For example, Japanese patent application postpones open No.321569/1998 openly, and the polishing speed of silicon oxide film can be controlled by the above-mentioned composition that is used to polish, and increases polishing and removal selectivity at polysilicon film and silicon oxide film like this.But the polishing speed of nitride is not controlled in research.

Also disclose a kind of composition that is used to polish, wherein combination comprises tetramethyl ammonium, alkali and hydrogen peroxide.The polishing speed that allegedly utilizes said composition may command nitride is to increase polishing and the removal selectivity (for example, Japanese patent application postpones open No.270401/1998) at oxide compound and nitride.But said composition have excellent at oxide compound and nitride polishing and remove selectivity, but not have research at the polishing of polycrystalline (becoming the material of gate electrode) and nitride and removal selectivity with at the polishing and the removal selectivity of polycrystalline and silicon oxide.

For the above-mentioned composition that is used to polish, especially, do not have the permanent stability of research under the high density state, but wherein the concentration of respective components is higher than the polishing adaptive state that is actually used in polishing, and said composition is set at use in the preparation composition several hrs afterwards.Therefore, said composition comprises the factor of actual use cost increase aspect, as needs therein concentration of component controlled and be low to moderate the transmission and storing down of its state when using.

Summary of the present invention

The present invention is based on that afore-mentioned is carried out and its first purpose provides a kind of water dispersion that is used for chemically machinery polished, it has excellent surface planarization ability and for example bends by the recessed of surface of chemically machinery polished, erosion or similar phenomenon reduce in planarization steps, have excellent at polycrystalline and silicon oxide polishing and remove selectivity and at the polishing of polycrystalline and nitride with remove selectivity, even under the high density state, have excellent permanent stability; Use the said composition CMP (Chemical Mechanical Polishing) process; Production technique with semiconductor devices.

Second purpose of the present invention provides a kind of water dispersion that is used for chemically machinery polished, like this by chemically machinery polished, polished surface is recessed to be bent, corrodes or comprise that the surface imperfection of scratch is suppressed in planarization steps, and it have excellent at polycrystalline and silicon oxide polishing and remove selectivity and at the polishing of polycrystalline and nitride with remove selectivity, even under the high density state, have excellent permanent stability; Use the said composition CMP (Chemical Mechanical Polishing) process; Production technique with semiconductor devices.

According to the present invention, therefore provide by with soluble quaternary ammonium, inorganic acid salt and abrasive grain are sneaked into water medium and first water dispersion that is used for chemically machinery polished (following also be called " first slurry ") that obtains.

According to the present invention; also providing a kind of passes through at least a soluble quaternary ammonium; it is not another alkaline organic compound of this soluble quaternary ammonium; inorganic acid salt, water-soluble polymers and abrasive grain are sneaked into water medium and second water dispersion that is used for chemically machinery polished (following also be called " second slurry ") that obtains.

According to the present invention, further provide a kind of preparation to be used for the material of the water dispersion of chemically machinery polished, comprise by at least a soluble quaternary ammonium and inorganic acid salt are sneaked into first aqueous dispersion materials (I) that water medium obtains, with by another alkaline organic compound of at least a water-soluble polymers and water-insoluble quaternary ammonium salt being sneaked into second aqueous dispersion materials (II) that water medium obtains, wherein abrasive grain is sneaked at least a in first aqueous dispersion materials (I) and second aqueous dispersion materials (II), and the water dispersion that is used for chemically machinery polished obtains by first aqueous dispersion materials (I) and second aqueous dispersion materials (II).

According to the present invention, a kind of CMP (Chemical Mechanical Polishing) process further is provided, comprise want polished surface is used the above-mentioned any water dispersion polishing that is used for chemically machinery polished.

CMP (Chemical Mechanical Polishing) process can further comprise, another that polished surface is used the water dispersion that is used for chemically machinery polished more than non-is used for water dispersion polishing of chemically machinery polished.

According to the present invention, a kind of production process for semiconductor devices that is used for further is provided, wherein semiconductor devices by with on the semiconductor substrate the polished surface of wanting use the above-mentioned any water dispersion polishing that is used for chemically machinery polished to produce.

Detailed description of the preferred embodiments

Below describe according to the chemically machinery polished water dispersion (following also be called simply " slurry ") that is used for of the present invention.

According to the present invention, mainly provide first slurry and second slurry.

＜the first slurry 〉

First slurry passes through the water soluble quaternary ammonium salt, and inorganic acid salt and abrasive grain are sneaked into water medium and obtained.

Below describe the respective components that constitutes first slurry in detail.

First slurry can standing storage under high density state as described below.But the preferred blending ratio of respective components described below (following also be called " specific blend ratio ") but be all values of the polishing adaptive state that is used for polishing.

[1] soluble quaternary ammonium:

Soluble quaternary ammonium is preferably the compound of following structural formula (1) expression

[NR ₄] ⁺[OH] ^-????????(1)

Wherein R is the alkyl with 1-4 carbon atom.

By the way, 4 R bases can be same to each other or different to each other.

Its object lesson comprises compound such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, tetra isopropyl ammonium hydroxide, TBAH and four isobutyl-ammonium hydroxide.Wherein, Tetramethylammonium hydroxide and tetraethyl ammonium hydroxide are especially preferred.

Above-mentioned soluble quaternary ammonium can separately or be used in combination.

The blending ratio of soluble quaternary ammonium is preferably the 0.005-5% quality, more preferably 0.008-4% quality, and especially preferred 0.01-3% quality is based on the total mass of first slurry.If the blending ratio of soluble quaternary ammonium is lower than 0.005% quality, can not realize enough polishing speeds in some cases.Need not to comprise the soluble quaternary ammonium that ratio surpasses 5% quality.

By the way, soluble quaternary ammonium is dissolved in the gained water dispersion that is used for chemically machinery polished, and its part is involved as ion.

[2] inorganic acid salt:

The example of inorganic acid salt comprises sodium salt, sylvite, ammonium salt mineral acid such as spirit of salt, nitric acid, sulfuric acid, carbonic acid and phosphoric acid; And sodium salt, sylvite and ammonium salt have the hydrosulphuric acid salt ion, bicarbonate ion or hydrogen orthophosphate ion.Wherein, ammonium salt is preferred, volatile salt wherein, and ammonium nitrate and ammonium sulfate are especially preferred.These inorganic acid salts can separately or be used in combination.

The blending ratio of inorganic acid salt is preferably the 0.005-5% quality, more preferably 0.008-4% quality, and especially preferred 0.01-3% quality is based on the total mass of first slurry.

If the blending ratio of inorganic acid salt is lower than 0.005% quality, control recessed curved and erosive effect, that is, reduce recessed bending and may become not enough in some cases with the erosive effect.Need not to comprise the inorganic acid salt that ratio surpasses 5% quality.

[3] abrasive grain:

Abrasive grain comprises inorganic particle, organic granular and composite particles.

As the example of inorganic particle, can mention silicon-dioxide, aluminum oxide, cerium oxide, titanium oxide, zirconium white, silicon nitride, the particle of Manganse Dioxide and analogue.Wherein, silica granules is preferred.

Object lesson as silicon oxide particle, can mention by pyrolytic process synthetic fumed silica, wherein silicon chlorides or analogue and oxygen and hydrogen react in vapor phase, by sol-gel technology synthetic colloidal silica, wherein metal alkoxide hydrolysis and condensation, with by mineral colloid technology synthetic colloidal silica, wherein impurity is removed by purifying.

Be in wherein primary particle combination or accumulative state in water medium by sol-gel technology or colloid technology synthetic colloidal silica, that is, and at the state of secondary granule, if its particle diameter is less.The inorganic particle that is in this state preferably has average particulate diameter 1-3,000nm, and more preferably 2-1,000nm is in primary particle.

The average particulate diameter of secondary granule is preferably 5-5,000nm, more preferably 5-3,000nm, especially preferred 10-1,000nm.If use the inorganic particle of the average particulate diameter of its secondary granule less than 5nm, the gained water dispersion that is used for chemically machinery polished can not be realized enough high polishing speeds in some cases so.On the other hand, surpass 5 for the average particulate diameter that uses its secondary granule, the inorganic particle of 000nm prevents that to recessed curved and erosive effect from can become not enough and in addition in some cases, tends to occur surface imperfection such as scratch.

The average particulate diameter of primary particle can be by the observed value of expection particulate specific surface area and the observations of mode transmission electron microscope, waits and calculates.The average particulate diameter of secondary granule can utilize laser light scattering diffractometry equipment, or analogue and measuring.

On the other hand, inorganic particle is as passing through the form production of pyrolytic process synthetic silica with secondary granule, and be very difficult in water medium they are separated into the primary particle state, so these particles are as existing by assembling the secondary granule that primary particle obtains.Therefore, the inorganic particle that is formed by pyrolytic process institute synthetic silica enough uses, as long as stipulate its secondary granule.

As by in the pyrolytic process synthetic silica, the average particulate diameter of its secondary granule is preferably 10-10 at inorganic particle, 000nm, more preferably 20-7,000nm, especially preferred 50-5,000nm.By using the inorganic particle of forming by fumed silica (average particulate diameter of its secondary granule falls in this scope), a kind of high polishing speed of realizing can be provided, fully prevent the recessed slurry of bending and corroding and have high stability.

Example as organic granular, can mention the polymer beads of forming by following material respectively: (1) polystyrene and styrol copolymer, (2) (methyl) acrylate copolymer and (methyl) acrylic copolymer such as polymethylmethacrylate, (3) polyvinyl chloride, polyacetal, saturated polyester, polymeric amide, polyimide, polycarbonate and phenoxy resin and (4) polyolefine and olefin copolymer such as polyethylene, polypropylene, poly-(1-butylene) and poly-(4-methyl-1-pentene), and other thermoplastic resin.

These organic granulars can be by grinding by emulsion polymerization technology, suspension polymerization technology, emulsion dispersion body polymerization technology, the method for the resin that bulk polymerization technology or similar technology obtain, or other method and making.Organic granular also can be the particle with multipolymer of crosslinking structure, and described result obtains by crosslinkable monomers such as Vinylstyrene or ethylene glycol dimethacrylate are coexisted in above-mentioned polymerization technology.

Organic granular is preferably (1) polystyrene of being selected from the above-mentioned resin and styrol copolymer and (2) (methyl) acrylate copolymer and (methyl) acrylic copolymer such as the resin of polymethylmethacrylate and its multipolymer with crosslinking structure.

In aforesaid these organic granulars, its nearly all particle generally exists as the simple particle in the slurry.The average particulate diameter of these organic granulars is preferably 10-5,000nm, more preferably 15-3,000nm, especially preferred 20-1,000nm.By using the organic granular of average particulate diameter in this scope, a kind of high polishing speed of realizing can be provided, fully prevent the recessed water dispersion that is used for chemically machinery polished of bending and corroding and have high stability.

In the present invention, as the object lesson of composite particles, can mention by organic granular and inorganic particle being integrated the inorganic organic composite granulated and gained that obtains by modified material being keyed to the particle of the modification that obtains on the surface of organic granular.

By organic organic composite granulated composite particles of forming is to make these particles be not easy to separate those that obtain by organic granular is integrated with inorganic particle.Be not particularly limited the kind of these organic granulars and inorganic particle.For example, can use above-mentioned identical organic granular and inorganic particle.

Be not particularly limited the concrete structure of composite particles.For example, preferably use by combining those that obtain with inorganic particle by suitable method by the organic granular that polymer beads is formed.

More specifically, the ζDian Shi polarity that is in wherein organic granular and inorganic particle is different states mutually, exist by electric electrostatic force, and for example, the bonded particle can be used as composite particles in the water medium.

The ζDian Shi of organic granular is in whole pH scope or get rid of in the wide pH scope of low pH scope normally negative value.Especially, by having carboxyl, the organic granular that the polymkeric substance of sulfonic acid group or analogue is formed has negative ζDian Shi certainly and has positive ζDian Shi by the organic granular that the polymkeric substance with amino or analogue is formed in specific pH scope.On the other hand, the ζDian Shi of inorganic particle has high pH dependency and some inorganic particles have iso-electric point at characteristic pH place, and this moment, ζDian Shi was zero.In these inorganic particles, the polarity of its ζDian Shi is counter-rotating down at that point.

According to the above-mentioned fact, the organic granular of particular types is combined with the inorganic particle of particular types, and two kinds of particles mixed in certain pH scope make its ζDian Shi become mutually opposite polarity, can obtain so wherein these organic granulars and inorganic particle by electric electrostatic force be integrated inorganic organic composite granulated.Even the ζDian Shi of blended organic granular and inorganic particle has identical polarity when mixing, by after mixing, change pH with generation wherein its ζDian Shi become mutually opposite polar state, what can obtain also that wherein organic granular and inorganic particle integrated is inorganic organic composite granulated.

In the present invention, composite particles can be the organic granular of modification, wherein suitable modified material for example be keyed to by, on the surface of the organic granular that polymer beads is formed.As the example of polymer beads, can mention the particle of polystyrene and polymethylmethacrylate.The polymer beads that has been linked with modified material on it can pass through, for example following method obtains, the reactive explosive that wherein is used for modified material, as organoalkoxysilane, aluminium-alcohol salt or titanium alkoxide exist under the situation of polymer beads polycondensation to form modified material on the surface at polymer beads.

If being used for the material of modified material is organoalkoxysilane, can obtain the organic granular that polymer beads wherein has the modification of polysiloxane in its surface.On the other hand, be aluminium-alcohol salt or titanium alkoxide if be used for the material of modified material, can obtain having the organic granular of the modification of the atomic group that comprises aluminium or titanium atom.In aforesaid method, also available silane coupling agent in the surface of polymer beads or analogue are handled.

In the present invention, composite particles is also by being keyed to inorganic particle such as silica granule or alumina particle by on the surface of the organic granular of suitable polymers granulometric composition and bonded is inorganic organic composite granulated.In this case, inorganic particle can physical form be connected on lip-deep adhesion component of polymer beads such as the polysiloxane or the chemical bonding by being present in lip-deep functional group of polymer beads such as hydroxyl.

Wherein inorganic organic composite granulated as mentioned above by electric electrostatic force integration, the material that has been modified for example passes through, organoalkoxysilane, those of aluminium-alcohol salt, titanium alkoxide or the analogue modification there being polycondensation under these inorganic organic composite granulated situations also can be used as composite particles.

If composite particles is by inorganic organic composite granulated the composition, these composite particles exist with any following state (1)-(3) according to the particle diameter and the component ratio of corresponding organic granular that forms composite particles and inorganic particle, or exist with the state that wherein has more than one states.

State (1): wherein inorganic particle as the shell particle adhesion to the surface of the nuclear particle of forming by organic granular.

State (2): wherein organic granular as the shell particle adhesion to the surface of the nuclear particle of forming by inorganic particle.

State (3): wherein organic granular and inorganic particle are assembled mutually and are not formed transparent nucleocapsid structure.

In above-mentioned state, state (1) or (3) are preferred.

In each state (1)-(3), inorganic particle can be the primary particle and the secondary granule of any state, or two kinds of particles can mix.

For forming the inorganic organic composite granulated inorganic particle and the component ratio of organic granular, the ratio of inorganic particle is preferably 1-2,000 mass parts, more preferably 10-1,000 mass parts/100 mass parts organic granulars.

In the present invention, the average particulate diameter of composite particles is preferably 20-20,000nm, more preferably 50-10,000nm, especially preferred 50-5,000nm.

By comprising the composite particles that satisfies above-mentioned condition, a kind of high polishing speed of realizing can be provided, fully prevent the recessed slurry of bending and corroding and have high stability.

The blending ratio may command of abrasive grain is to preferred 0.01-10% quality, more preferably 0.03-8% quality, and especially preferred 0.05-5% quality is based on the total mass of first slurry.If the blending ratio of abrasive grain is lower than 0.01% quality, the gained slurry can not be realized enough polishing speeds.On the other hand, if blending ratio surpasses 10% quality, the gained slurry becomes expensive and stability in storage variation in some cases.

[4] water medium:

First slurry is by with aforesaid soluble quaternary ammonium, and inorganic acid salt and abrasive grain and the component that optionally comprises are sneaked in the water medium they are dispersed in the water medium and obtained.As water medium, can make water, comprise the blending agent that water and its amount or ratio are not damaged the water-soluble alcohol of polishing performance, or analogue.But water is especially preferred.

[5] other component:

First slurry passes through as mentioned above with soluble quaternary ammonium, and inorganic acid salt and abrasive grain are sneaked into water medium and obtained and additive such as organic acid or its salt, oxygenant and/or the tensio-active agent that can comprise as required except said components.Also can comprise the water soluble polymkeric substance.

The organic acid object lesson comprises formic acid, acetate, propionic acid, p-toluenesulphonic acids; isoprene sulfonic acid, gluconic acid, lactic acid, citric acid; tartrate, oxysuccinic acid, oxyacetic acid; hexanodioic acid, propanedioic acid, oxalic acid; succsinic acid, fumaric acid, toxilic acid and phthalic acid; and be amino acid whose L-Ala, glycine, aspartic acid and glycyl glycine.

Organic acid salt comprises above-mentioned organic acid an alkali metal salt such as sylvite and ammonium salt.

These organic acids or its salt can separately or be used in combination.In addition, organic acid and salt can be used in combination.

The blending ratio may command of organic acid or its salt is to preferred maximum 1% quality, and more preferably maximum 0.5% quality are based on the total mass of first slurry.

The organic acid blending ratio is controlled in the above-mentioned scope, and the gained slurry can be realized enough polishing characteristics and become stable like this.

The object lesson of oxygenant comprises hydrogen peroxide, organo-peroxide such as peracetic acid, peroxybenzoic acid and t-butyl hydroperoxide, nitrate compound such as nitric acid and iron nitrate, perhalogenation compound such as perchloric acid, persulphate such as ammonium persulphate, polyvalent metal salt such as iron nitrate and ceric ammonium nitrate, with heteropolyacid such as silicotungstic acid, phospho-wolframic acid, silicomolybdic acid and phospho-molybdic acid.Wherein, hydrogen peroxide and organo-peroxide (wherein containing metal element and its degradation production are not harmless) are preferred.By comprising these oxygenants, polishing speed can greatly improve, especially, if metallic membrane that polishing forms on wafer such as film to be processed.

These oxygenants can separately or be used in combination.

The blending ratio may command of oxygenant is to maximum 15% quality, preferred 0.001-15% quality, and more preferably 0.03-10% quality, especially preferred 0.01-8% quality is based on the total mass of first slurry.

The blending ratio of oxygenant is controlled in the above-mentioned scope, and the gained slurry can be realized enough high polishing speeds like this.

As tensio-active agent, can mention cats product, anion surfactant, nonionogenic tenside and amphoterics.

Wherein, anion surfactant and nonionogenic tenside are preferred.

The object lesson of cats product comprises aliphatic amine salt and aliphatic ammonium salt.

The object lesson of anion surfactant comprises carboxylate salt such as fatty acid soaps and alkyl ether carboxy acid salt, sulfonate such as alkylbenzene sulfonate, sulfonated alkyl naphathalene and sulfonated, vitriol such as higher alcohol sulfate and sulfated alkyl ether and phosphoric acid salt such as alkylphosphonic.

The object lesson of nonionogenic tenside comprises ether type tensio-active agent such as polyoxy ethylidene alkyl oxide, the polyoxy ethyleneether of Etheric ester type tensio-active agent such as glyceryl ester, ester type tensio-active agent such as cithrol, glyceryl ester and Isosorbide Dinitrate, acetylenediol and its ethylene oxide adduct, and acetylene alcohol.The object lesson of amphoterics comprises alkyl betaine and amine oxide.

These tensio-active agents can separately or be used in combination.Also can be used in combination different types of tensio-active agent.

The blending ratio of tensio-active agent can preferably be controlled to maximum 1% quality, and more preferably maximum 0.5% quality are based on the total mass of first slurry.The blending ratio of tensio-active agent is controlled in the above scope, and the gained slurry can be realized enough polishing characteristics and become stable like this.

The object lesson of water-soluble polymers comprises Mierocrystalline cellulose, carboxy methyl cellulose, hydroxy ethyl cellulose, polyoxyethylene glycol, polyethylene imine based and polyacrylic acid and its salt.

These water-soluble polymerss can separately or be used in combination.

The blending ratio may command of water-soluble polymers is to preferred maximum 1% quality, and more preferably maximum 0.5% quality are based on the total mass of first slurry.

The blending ratio of water-soluble polymers is controlled in the above scope, and the gained slurry can be realized enough polishing characteristics and become stable like this.

These additives that optionally comprise as required can mix when preparation first slurry, or also can or mix by its aqueous solution of independent preparation when implementing chemical-mechanical polishing step on the polishing block in the supply line of first slurry.

The preferred pH of first slurry changes along with the kind of the film that will polish.For example, if polishing monocrystalline silicon membrane or polysilicon film, preferred pH scope is 7-13, more preferably 9-12.If pH is lower than 7, can not realize enough polishing performances in some cases.

On the other hand, if pH surpasses 13, but variation in some cases under the temperature of slurry self.First slurry does not preferably have too low or high pH.

In order to regulate the pH of first slurry, can use acid or alkali.The example of available alkali comprises potassium hydroxide and ammonia.

As the film with the polishing of first slurry, preferably silicon type film.Its object lesson comprises amorphous silicon film, monocrystalline silicon membrane, polysilicon film, silicon nitride film and analogue.

If silicon type film is polysilicon film or amorphous silicon film, arsenic and phosphorus or analogue can be doped in polycrystalline and/or the amorphous silicon, these films of corresponding formation.

If chemically machinery polished uses first slurry to carry out, soluble quaternary ammonium is used in polishing, and the blending ratio of the respective components of inorganic acid salt and abrasive grain and the component that optionally comprises falls into the interior slurry of above-mentioned specific blend proportional range.First slurry that is used for this polishing can be by making respective components according to mixing corresponding to the amount of specific blend ratio.In addition, but but prepared beforehand wherein the concentration of respective components be higher than the high density product of the specific blend ratio in the polishing adaptive state that is actually used in polishing and this high density product can be when polishing water or analogue dilution make the blending ratio of respective components reach the specific blend ratio.

The high density product of first slurry obtains by respective components being mixed the ratio ranges make the ratio ranges of blending ratio of relevant respective components equal relevant specific blend ratio, and respective components blending ratio at this moment makes that preferably soluble quaternary ammonium is maximum 10% quality, inorganic acid salt is maximum 10% quality, with abrasive grain be maximum 20% quality, all based on the total mass of high density product.

First slurry can have initial polishing performance by diluting as required after prolonged storage in chemical-mechanical polishing step when it uses, even but this slurry be by with respective components according to mixing the slurry under the polishing adaptive state of making corresponding to the amount of specific blend ratio or being in slurry under the high density state.

For example, after storing 30 days under 40 ℃ under the high density state or also diluting in 90 days, first slurry can have initiation performance, even it is used for polishing step.

By the way, term " initial " is meant after mixing respective components lapse of time of several hrs (1-5 hour) soon.

[6] want the chemically machinery polished of polished surface:

First CMP (Chemical Mechanical Polishing) process according to the present invention comprises, with first slurry polishing polished surface of wanting.If the chemically machinery polished of the polished surface of wanting uses first slurry to carry out, commercially available chemical mechanical polishing apparatus such as model " EPO-112 " or model " EPO-222 " (making) by Ebara company; Model " Mirra " (making) by Applied Materials; Or analogue is used under the polishing condition of regulation and polishes.

First CMP (Chemical Mechanical Polishing) process embodiment according to the present invention, for example, groove part forms on semiconductor substrate, polysilicon film forms on the whole surface of the semiconductor substrate that comprises this groove, polysilicon film uses the aforesaid this chemical mechanical polishing apparatus and first slurry to stand polished finish to remove the other parts be not embedded in the polysilicon film in the groove part subsequently, has excellent surface property like this and can be formed in the groove part on being formed at semiconductor substrate by the embedding groove that polycrystalline is formed.

According to another embodiment, silicon oxide film is forming on the semiconductor substrate and groove part forms on the gained stacked film in addition.After polysilicon film further is deposited in the groove part that is formed on the stacked film, sedimentary polysilicon film uses silicon oxide film to carry out polished finish as barrier layer, and will handle as want polished surface by the surface that this polished finish exposes, use, for example, the above-mentioned chemical mechanical polishing apparatus and first slurry carry out polished finish, have excellent surface property like this and can in the groove part on being formed at stacked film (obtaining), form, because first slurry has excellent polishing and removal selectivity at polysilicon film and silicon oxide film by silicon oxide film is stacked on the semiconductor substrate by the embedding groove that polycrystalline is formed.In this embodiment, even polished finish is carried out according to the mode identical with described embodiment, just form nitride film and substitute silicon oxide film, be used as barrier layer with this nitride film, have excellent surface property and can in the groove part on being formed at stacked film (obtaining), form, because first slurry has excellent polishing and removal selectivity at polysilicon film and nitride film by nitride film is stacked on the semiconductor substrate by the embedding groove that polycrystalline is formed.

According to further embodiment, monocrystalline silicon membrane can use the above-mentioned chemical mechanical polishing apparatus and first slurry to be polished to mirror status.

According to further embodiment, groove part forms on semiconductor substrate, the wiring material film forms on the whole surface of the semiconductor substrate that comprises this groove, and chemical mechanical polish process uses the above-mentioned chemical mechanical polishing apparatus and first slurry to carry out the other parts that are not embedded in the wiring material film in the groove part to remove subsequently, and the embedding wiring that has excellent surface property like this can form in the groove part on being formed at semiconductor substrate.

Polishing at polysilicon film and silicon oxide film can be polished under identical condition by the corresponding membrane that will will polish respectively and mutual the comparison with the removal selectivity with the removal selectivity with at the polishing of polysilicon film and nitride film, particularly, assess by the ratio of determining the polishing speed between two films.Term " identical condition " is meant, uses the burnishing device of specific model, and makes worktable and its speed of rotation, polish pressure, and polishing time, the unit time feeding quantity of the kind of used polishing pad and the water dispersion that is used for chemically machinery polished is identical." ratio of polishing speed " can be by polysilicon film, and the value of the corresponding polishing speed of silicon oxide film and nitride film is calculated, and wherein these films polish under identical condition respectively.

The example of nitride film comprises silicon nitride film, titanium nitride film and nitrogenize tantalum film.

In the present invention's first CMP (Chemical Mechanical Polishing) process, the first specific polishing speed ratio that is expressed as polysilicon film polishing speed and the ratio of silicon oxide film polishing speed therein silicon oxide film and polysilicon film under the situation of polishing under the identical condition may command at least 30, preferably at least 100, especially preferably at least 300.In addition, the second specific polishing speed ratio that is expressed as polysilicon film polishing speed and the ratio of nitride film polishing speed therein nitride film and polysilicon film under the situation of polishing under the identical condition may command at least 50, preferably at least 100, especially preferably at least 300.

After finishing polished finish, the preferred abrasive grain of staying on the glazed surface of removing.The removal of abrasive grain can be undertaken by common cleaning method.For example, cleaning is used and is comprised about 1: 1: 5 ammonia of respective quality ratio, and the alkaline detergent solution of hydrogen peroxide and water carries out after brush cleans, and can remove the abrasive grain that adheres on the glazed surface like this.

In order to remove the foreign metal material that is adsorbed onto on the glazed surface, cleaning for example can be used, by aqueous citric acid solution, the washing soln that the mixed aqueous solution of the mixed aqueous solution of hydrofluoric acid and citric acid or hydrofluoric acid and ethylene diamine-tetraacethyl (EDTA) is formed carries out.

If abrasive grain only is made up of organic granular, glazed surface also can be heated to high temperature existing under the situation of oxygen, burns like this and removes organic granular on the glazed surface.As the example of specific combustion method, can mention by oxygen plasma being played a role or supplying with the ashing treatment that oxyradical carries out by flowing downward.By this method, can remove the organic granular of staying on the glazed surface easily.

[7] production technique of semiconductor devices:

First production technique according to semiconductor devices of the present invention is the technology that a kind of use first slurry is produced semiconductor devices.Term " semiconductor devices " broadly is meant polished wafer, is furnished with this wafer or is fixed with the various device of this wafer and is furnished with the various device (that is, being combined with the various device of this base material) of the base material of being made by this wafer.

＜the second slurry 〉

Second slurry passes through at least a soluble quaternary ammonium, another alkaline organic compound of water-insoluble quaternary ammonium salt, and inorganic acid salt, water-soluble polymers and abrasive grain are sneaked into water medium and are obtained.

Below describe second slurry in detail.

Second slurry is to comprise soluble quaternary ammonium at least, another alkaline organic compound of water-insoluble quaternary ammonium salt, inorganic acid salt, water-soluble polymers, the slurry form that contains all components of abrasive grain and water medium or the biliquid mixed type slurry form supply of forming by the material that is used to prepare the water dispersion that is used for chemically machinery polished. comprises by at least a soluble quaternary ammonium and inorganic acid salt are sneaked into the first aqueous dispersion materials (I) that aqueous medium obtains for the preparation of the material of the aqueous dispersion that is used for chemically mechanical polishing; With by another alkaline organic compound of at least a water-soluble polymer and water-insoluble quaternary ammonium salt being sneaked into the second aqueous dispersion materials (II) that aqueous medium obtains, wherein the abrasive grain aqueous dispersion of being sneaked at least a in the first aqueous dispersion materials (I) and the second aqueous dispersion materials (II) and being used for chemically mechanical polishing is made by the first aqueous dispersion materials (I) and the second aqueous dispersion materials (II).

Second slurry can standing storage under the high density state as described below.But but the preferred specific blend ratio of respective components described below is all values of the polishing adaptive state that is used for polishing.

[1] another alkaline organic compound of soluble quaternary ammonium and water-insoluble quaternary ammonium salt:

The slurry that contains all components comprises another alkaline organic compound of soluble quaternary ammonium and water-insoluble quaternary ammonium salt.

In biliquid mixed type slurry, the water soluble quaternary ammonium salt is included in first aqueous dispersion materials (I), and another alkaline organic compound of water-insoluble at least quaternary ammonium salt is included in second aqueous dispersion materials (II) simultaneously.This second aqueous dispersion materials (II) can further comprise soluble quaternary ammonium.

As soluble quaternary ammonium, preferably use the season alkylammonium salt, and season alkylammonium salt be preferably the compound that is expressed as following structural formula (1)

[NR ₄] ⁺[OH] ^-????????(1)

Wherein R is the alkyl with 1-4 carbon atom.

By the way, 4 R groups can be identical or different mutually.

As its object lesson, the identical compound that is exemplified when for example mentioning with the soluble quaternary ammonium that constitutes first slurry.Wherein, Tetramethylammonium hydroxide and tetraethyl ammonium hydroxide especially preferably use.

The example of another alkaline organic compound of water-insoluble quaternary ammonium salt comprises water-soluble amine.

The example of water-soluble amine comprises (1) alkylamine such as methylamine, dimethyl amine, Trimethylamine, ethylamine, diethylamide and triethylamine, (2) alkanolamine such as diethanolamine, trolamine and amino ethyl ethanolamine, (3) alkylene amines such as diethylenetriamine, Triethylenetetramine (TETA).Tetren, penten and triethylenediamine and (4) imines such as ethylenimine.Wherein, diethanolamine, trolamine and analogue preferably use.

The salt of any above-mentioned amine can be used as water-soluble amine.

Water-soluble amine can separately or be used in combination.

The blending ratio of another alkaline organic compound of soluble quaternary ammonium and water-insoluble quaternary ammonium salt (following also be called " specific alkaline organic compound ") can be the 0.005-10% quality, preferred 0.005-8% quality, more preferably 0.008-5% quality, especially preferred 0.01-4% quality is based on the total mass of second slurry of slurry that contains all components or biliquid mixed type slurry form.If the blending ratio of specific alkaline organic compound is lower than 0.005% quality, can not realize enough polishing speeds in some cases.Need not to comprise the specific alkaline organic compound that ratio surpasses 10% quality.

Specific alkaline organic compound is dissolved in the slurry, and its part comprises as ion.

[2] inorganic acid salt:

As inorganic acid salt, any compound that is exemplified when can be used as the inorganic acid salt that constitutes first slurry.

The blending ratio of inorganic acid salt can be the 0.005-8% quality, preferred 0.005-6% quality, and more preferably 0.008-4% quality, especially preferred 0.01-3% quality is based on the total mass of second slurry of slurry that contains all components or biliquid mixed type slurry form.

If the blending ratio of inorganic acid salt is lower than 0.005% quality, prevent that recessed bending with the erosive effect from can become not enough in some cases.Need not to comprise the inorganic acid salt that ratio surpasses 8% quality.

[3] water-soluble polymers:

The example of water-soluble polymers comprises derivatived cellulose such as methylcellulose gum, methyl hydroxyl ethyl cellulose, methyl hydroxy propyl cellulose, hydroxy ethyl cellulose, hydroxy propyl cellulose, carboxy methyl cellulose, carboxy ethyl Mierocrystalline cellulose and carboxyl methyl hydroxyl ethyl cellulose; Polysaccharide such as chitosan; And water-soluble polymers such as polyoxyethylene glycol, polyethylene imine based, Polyvinylpyrolidone (PVP), polyvinyl alcohol, polyacrylic acid and its salt, polyacrylamide and polyoxyethylene.Wherein, derivatived cellulose and polyacrylic acid and its salt are preferred, and wherein hydroxy ethyl cellulose and carboxy methyl cellulose are preferred.

These water-soluble polymerss can separately or be used in combination.

The blending ratio of water-soluble polymers can be the 0.001-5% quality, preferred 0.001-3% quality, more preferably 0.003-2% quality, especially preferred 0.005-1% quality is based on the total mass of second slurry of slurry that contains all components or biliquid mixed type slurry form.

If the blending ratio of water-soluble polymers is lower than 0.001% quality, prevent that recessed bending with the erosive effect from can become not enough in some cases, and surface imperfection can increase.Need not to comprise the water-soluble polymers that ratio surpasses 5% quality.

[4] abrasive grain:

In second slurry, abrasive grain is involved as the basal component that contains in the slurry of all components, and is comprised at least a in first aqueous dispersion materials (I) and second aqueous dispersion materials (II) in biliquid mixed type slurry.

As abrasive grain, can use any particle that is exemplified when can be used as the particle of the abrasive grain that constitutes first slurry.

The blending ratio may command of abrasive grain is to the 0.01-10% quality, preferred 0.03-8% quality, and especially preferred 0.05-5% quality is based on the total mass of second slurry of slurry that contains all components or biliquid mixed type slurry form.If the blending ratio of abrasive grain is lower than 0.01% quality, the gained slurry can not be realized any enough polishing speeds.On the other hand, if blending ratio surpasses 10% quality, the gained slurry becomes expensive and in some cases can be in variation aspect the stability in storage.

[5] water medium:

Constitute that the slurry that contains all components of second slurry or first aqueous dispersion materials (I) in the biliquid mixed type slurry are corresponding with second aqueous dispersion materials (II) to be obtained so that they are dispersed in the water medium by above-mentioned respective components and the component that optionally comprises are sneaked in the water medium.As water medium, can make water, comprise its amount or ratio and do not damage the water of polishing performance and the blending agent of water-soluble alcohol, or analogue.But water is especially preferred.

[6] other component:

The slurry that contains all components passes through as mentioned above with soluble quaternary ammonium; another alkaline organic compound of water-insoluble quaternary ammonium salt; inorganic acid salt; water-soluble polymers and abrasive grain are sneaked into water medium and are obtained and can comprise additive such as organic acid or its salt as required, oxygenant and/or tensio-active agent and said components.

These other additives also can be included in the biliquid mixed type slurry.In this case, other additive can be included at least a in first aqueous dispersion materials (I) and second aqueous dispersion materials (II).

As organic acid and its salt, oxygenant and tensio-active agent, for example can mention with can be included in first slurry in those identical compounds.

In biliquid mixed type slurry, water-soluble polymers also can be included in first aqueous dispersion materials (I) as required.

The object lesson of water-soluble polymers is included in those polymkeric substance that exemplified when can be used as the polymkeric substance that constitutes second aqueous dispersion materials (II).

If water-soluble polymers is also contained in first aqueous dispersion materials (I), the total blending ratio that is included in the water-soluble polymers in first aqueous dispersion materials (I) and second aqueous dispersion materials (II) can be the 0.001-5% quality, preferred 0.001-3% quality, more preferably 0.003-2% quality, especially preferred 0.005-1% quality is based on the total mass of biliquid mixed type slurry.

The blending ratio of water-soluble polymers is controlled in the above scope, and the gained slurry can be realized enough polishing characteristics and become stable like this.

Under the situation of the slurry that contains all components, these additives that can optionally comprise as required can correspondingly mix when it prepares, or also can or mix by its aqueous solution of independent preparation when implementing chemical-mechanical polishing step on the polishing block in the supply line of this slurry.

Under the situation of biliquid mixed type slurry, these additives can correspondingly mix when preparation first aqueous dispersion materials (I) and second aqueous dispersion materials (II), can when mixing first aqueous dispersion materials (I), mix, or also can or when implementing chemical-mechanical polishing step, mix on the polishing block in the supply line of this slurry by its aqueous solution of independent preparation with second aqueous dispersion materials (II).

The preferred pH of second slurry is preferably in the scope identical with preferred pH scope in first slurry.

Example with the film of second slurry polishing comprises silicon type film such as silicon oxide film, polysilicon film, monocrystalline silicon membrane, amorphous silicon film and silicon nitride film, pure metal film such as pure tungsten film, pure aluminium film and fine copper film, with by tungsten, the alloy film of the alloy composition of aluminium or copper and any other metal.Also can mention by metal such as tantalum or titanium oxide compound such as tantalum oxide or titanium oxide, or the barrier layer (isolation layer) of nitride such as titanium nitride or tantalum nitride composition.Wherein, second slurry can be used for polishing suitably, especially, and silicon type film.

For above " polysilicon film " and " amorphous silicon film ", arsenic, phosphorus or analogue can be doped to respectively in polycrystalline and the amorphous silicon to form these films.This is equally applicable in the polysilicon film of other location expression of this specification sheets and amorphous silicon film.

If chemically machinery polished uses second slurry to carry out, the interior slurry of scope that respective components is as mentioned above used wherein in polishing and the blending ratio of the component that optionally comprises falls into the specific blend ratio carries out.Second slurry that is used for this polishing can be by making respective components according to mixing corresponding to the amount of specific blend ratio.In addition, but but prepared beforehand wherein the concentration of respective components be higher than the high density product of the concentration in the polishing adaptive state that is actually used in polishing and this high density product can be when polishing water or analogue dilution make the blending ratio of respective components reach the specific blend ratio.

The high density product of second slurry obtains by respective components being mixed the ratio ranges make the ratio ranges of blending ratio of relevant respective components equal relevant specific blend ratio, and respective components blending ratio at this moment makes that preferably soluble quaternary ammonium is maximum 10% quality, inorganic acid salt is maximum 10% quality, with abrasive grain be maximum 20% quality, all based on the total mass of high density product.

Second slurry can have initial polishing performance by diluting as required after prolonged storage in chemical-mechanical polishing step when it uses, even but this slurry be by with respective components according to mixing the slurry under the polishing adaptive state of making corresponding to the amount of specific blend ratio or being in slurry under the high density state.

For example, after storing 30 days under 40 ℃ under the high density state or also diluting in 90 days, second slurry can have initiation performance, even it is used for polishing step.

If biliquid mixed type slurry is used to carry out chemical-mechanical polishing step, first aqueous dispersion materials (I) and second aqueous dispersion materials (II) can be mixed for the slurry charge line, but or separate charging to the polishing block of chemical mechanical polishing apparatus be mixed for polishing block.In addition, first aqueous dispersion materials (I) and second aqueous dispersion materials (II) also can be mixed the gained mixture is stored in jar or the analogue before using in advance.In this case, this mixture can preferably use before the bad stability of biliquid mixed type slurry.

Be not particularly limited the ratio of first aqueous dispersion materials (I) and second aqueous dispersion materials (II), recessed curved as long as realize the polishing speed of expection, fully prevent erosion, scratch and similar phenomenon, and realize excellent stability.But first aqueous dispersion materials (I) is preferably 30/70-70/30 with the ratio [(I)/(II)] of second aqueous dispersion materials (II), in quality ratio.

[7] want the chemically machinery polished of polished surface:

Second CMP (Chemical Mechanical Polishing) process according to the present invention comprises with second slurry polishing polished surface of wanting.

If the chemically machinery polished of the polished surface of wanting uses second slurry to carry out, can under the polishing condition of regulation, polish as the burnishing device that burnishing device exemplified of first CMP (Chemical Mechanical Polishing) process that can be used for using first slurry.

Second CMP (Chemical Mechanical Polishing) process embodiment according to the present invention, for example, groove part is gone up at semiconductor substrate (also comprising semiconductor wafer) and is formed, silicon type film such as polysilicon film or amorphous silicon film form on the whole surface of the semiconductor substrate that comprises this groove, silicon type film uses the aforesaid this chemical mechanical polishing apparatus and second slurry to stand polished finish to remove the other parts be not embedded in the silicon type film in the groove part subsequently, has excellent surface property like this and the embedding groove be made up of silicon such as polysilicon film or amorphous silicon film can form in the groove part on being formed at semiconductor substrate.

According to another embodiment, silicon oxide film forms on the gained stacked film in addition in last formation of semiconductor substrate (also comprising semiconductor wafer) and groove part.After silicon such as polycrystalline or amorphous silicon further are deposited on the groove part that is formed on the stacked film, depositing silicon type film uses silicon oxide film to carry out polished finish as barrier layer, and handle as want polished surface by the surface that this polished finish exposes, use, for example, the above-mentioned chemical mechanical polishing apparatus and second slurry carry out polished finish, have excellent surface property like this and can in the groove part on being formed at stacked film (obtaining), form, because second slurry has excellent polishing and removal selectivity at silicon type film and silicon oxide film by silicon oxide film is stacked on the semiconductor substrate by the embedding groove that silicon is formed.In this embodiment, even polished finish is carried out according to the mode identical with described embodiment, just form nitride film such as titanium nitride film, nitrogenize tantalum film or silicon nitride film substitute silicon oxide film, be used as barrier layer with this nitride film, the embedding groove that has excellent surface property and is made up of silicon such as polysilicon film or amorphous silicon film can form in the groove part on being formed at stacked film (obtaining by nitride film is stacked on the semiconductor substrate), because second slurry has excellent polishing and removal selectivity at silicon type film and nitride film.

According to further embodiment of the present invention, can adopt the above-mentioned chemical-mechanical polisher and second slurry with specular polishing monocrystalline silicon membrane.

According to further embodiment, groove part is formed on the semiconductor substrate, wiring material film such as pure metal film such as pure tungsten film, pure aluminium film or fine copper film, or by tungsten, the alloy film alloy of the alloy composition of aluminium or copper and any other metal forms on the whole surface of the semiconductor substrate that comprises this groove, and polished finish uses the above-mentioned chemical mechanical polishing apparatus and second slurry to carry out the other parts that are not embedded in the wiring material film in the groove part to remove subsequently, and the embedding wiring that has excellent surface property like this can form in the groove part on being formed at semiconductor substrate.By the way, by metal such as tantalum or titanium, oxide compound such as tantalum oxide or titanium oxide, nitride forms on the surface that is formed at the groove on the semiconductor substrate as the barrier layer of titanium nitride or tantalum nitride or analogue composition, the wiring material film forms on the surface of barrier layer, and carries out polished finish subsequently.In this case, can form embedding wiring, because second slurry has excellent polishing and removal selectivity at wiring material film and barrier layer with excellent surface property.

Polishing and removal selectivity at polysilicon film or amorphous silicon film and silicon oxide film, polishing at silicon type film and nitride film can be polished under identical condition by the corresponding membrane that will will polish and mutual the comparison with the removal selectivity with the removal selectivity with at the polishing of wiring material film and barrier layer, particularly, assess by the ratio of determining the polishing speed between the film.Term " identical condition " is meant, uses the burnishing device of specific model, and makes worktable and its speed of rotation, polish pressure, and polishing time, the unit time feeding quantity of the kind of used polishing pad and the water dispersion that is used for chemically machinery polished is identical." ratio of polishing speed " can be by (1) silicon type film such as polysilicon film or amorphous silicon film, (2) become the silicon oxide film or the nitride film of barrier layer, (3) value of the corresponding polishing speed of wiring material film is calculated, and wherein these films polish under identical condition respectively.

In second CMP (Chemical Mechanical Polishing) process of the present invention, the first specific polishing speed ratio that is expressed as polysilicon film polishing speed and the ratio of silicon oxide film polishing speed therein silicon oxide film and polysilicon film under the situation of polishing under the identical condition may command at least 30, preferably at least 100, especially preferably at least 300.In addition, the second specific polishing speed ratio that is expressed as polysilicon film polishing speed and the ratio of nitride film polishing speed therein nitride film and polysilicon film under the situation of polishing under the identical condition may command at least 50, preferably at least 100, especially preferably at least 300.

After finishing polished finish, the preferred abrasive grain of staying on the glazed surface of removing.The removal of abrasive grain can be undertaken by exemplifying to the removal method of spendable removal method after finishing the chemically machinery polished of using first slurry.

[8] production technique of semiconductor devices:

Second production technique according to semiconductor devices of the present invention is a kind of technology of using above-mentioned second slurry to produce semiconductor devices.

[embodiment]

＜relate to the embodiment of first slurry 〉

[1] it is prepared to comprise the water dispersion of the abrasive grain of being made up of inorganic particle or composite particles:

(1) comprise the preparation of the water dispersion of inorganic particle:

(a) comprise the preparation of the water dispersion of fumed silica particle:

Fumed silica particle (Nippon Aerosil Co., the product of Ltd. with the 2kg amount; Trade(brand)name " Aerosil #50 ") adds 6.7kg ion exchanged water and utilize the ultra-sonic dispersion machine to disperse, and subsequently this dispersion is filtered the strainer with hole dimension 5 μ m, prepare the water dispersion that comprises fumed silica particle.The average primary particle diameter of the silica granule in this water dispersion is that 30nm and its average secondary granule diameter are 230nm.

(b) comprise the preparation of the water dispersion of colloidal silica:

To 2-rise the 70g aqueous ammonia of packing in the flask (concentration: 25% quality), 40g ion exchanged water, 175g ethanol and 21g tetraethoxysilane, and will under 180rpm stirs, be heated to 60 ℃.Under this temperature, after the continuously stirring 2 hours, its cooling is obtained the alcoholic dispersion of colloidal silica at mixture.Utilize vaporizer simultaneously to add ion exchanged water down and remove alcoholic acid technology and repeat several times, prepare and comprise the water dispersion that 20% quality has the colloidal silica of average primary particle diameter 35nm and average secondary granule diameter 70nm at 80 ℃.

Comprise the water dispersion that 20% quality has the colloidal silica of average primary particle diameter 15nm and average secondary granule diameter 25nm, with comprise the water dispersion that 20% quality has the colloidal silica of average primary particle diameter 70nm and average secondary granule diameter 150nm and prepare according to mode same as described above basically respectively in addition, just change the add-on of ethanol and tetraethoxysilane.

(2) comprise the preparation of the water dispersion of the abrasive grain of forming by composite particles:

(a) comprise the preparation of aqueous dispersion of polymer particles:

Rise 90 mass parts of packing in the flask (following " part ") methyl methacrylate, 5 parts of methoxy polyethylene glycol methacrylate-styrene polymer (products of Shin-Nakamura chemistry company limited of being called simply to 2-; Trade(brand)name " NK Ester M-90G; #400 "), 5 parts of 4-vinylpridines, 2 parts of azo-type initiators for polymerization (products of Wako Pure Chemical Industries Ltd., trade(brand)name " V50 ") and 400 parts of ion exchanged waters, and mixture under agitation is being heated to 70 ℃ to carry out polyreaction 6 hours under identical temperature under the nitrogen atmosphere, obtain comprising the aqueous dispersion of polymer particles with average particulate diameter 150nm like this, wherein said polymkeric substance has amino and polyglycol chain.The polyreaction productive rate is 95%.

(b) comprise the preparation of the water dispersion of composite particles:

Comprise aqueous dispersion of polymer particles that 10% quality obtains with 100 parts in above step (a) and add 2-and rises flask, add 1 part of methyltrimethoxy silane in addition, and with the gained mixture 40 ℃ of stirrings 2 hours down.Then, use the pH regulator to 2 of nitric acid, obtain water dispersion (1-a) this mixture.Comprise 10% quality colloidal silica (Nissan ChemicalIndustries, the product of Ltd.; Trade(brand)name " Snowtex O ", average primary particle diameter: the pH of water dispersion 10-20nm) uses potassium hydroxide to be adjusted to 8, obtains water dispersion (1-b).By the way, the ζDian Shi that is included in the poly methyl methacrylate particle in the water dispersion (1-a) is+17mV that the ζDian Shi that is included in the silica granule in the water dispersion (1-b) simultaneously is-40mV.

Add gradually and, the gained mixture was stirred 2 hours in addition at 50 parts of water dispersions (1-b), obtain comprising and have the colloidal silica particulate particulate water dispersion that is keyed on the polymer beads with after 100 parts of water dispersions (1-a) mix 2 hours.In this water dispersion, add 2 parts of vinyltriethoxysilanes, and mixture was stirred 1 hour.Then, add 1 part of tetraethoxysilane, and with mixture heating up to 60 ℃, continuously stirring 3 hours and with postcooling under this temperature obtains comprising the water dispersion of composite particles like this.The average particulate diameter of composite particles is 180nm.Composite particles make adhere to the lip-deep silica granule of polymer beads cover its 80%.

[2] be used for the preparation of high density product of the water dispersion of chemically machinery polished:

Ion exchanged water so that reaching the amount adding 1-of 100% quality, the total mass of gained high density product is risen polyethylene bottle, with concentration is that the tetramethylammonium hydroxide aqueous solution of 25% quality adds ion exchanged water to obtain concentration 6% quality, in Tetramethylammonium hydroxide content, and mixture fully stirred.Then, the aqueous solution (concentration:,, add 9% quality colloidal silica (average primary particle diameter: 35nm simultaneously that under agitation adds volatile salt in volatile salt content 20% quality) to obtain concentration 5.5% quality; Average secondary granule diameter: 70nm).After the gained mixture fully stirs, it is filtered the strainer with hole dimension 5 μ m, obtain the high density product [1Ad] of slurry [1A].

Corresponding high density product [1Bd]-[1Id] of slurry [1B]-[1I] obtains according to above-mentioned identical mode basically, and just the kind of respective components and combined amount are according to changing shown in the table 1.

Ion exchanged water so that reaching the amount adding 1-of 100% quality, the total mass of gained high density product is risen polyethylene bottle, and with the corresponding adding ion exchanged water of the aqueous solution shown in " additive 1 " row of table 2, obtain the corresponding combined amount shown in " additive 1 " row of table 2, and the gained mixture fully stirred.Then, the aqueous solution shown in " additive 2 " of table 2 row is under agitation added respectively, obtain the corresponding combined amount shown in " additive 2 " row of table 2.Simultaneously, add abrasive grain, the gained mixture fully stirs, and with strainer with hole dimension 5 μ m of they corresponding filtrations, obtains contrasting high density product [1ad]-[1ed] of slurry [1a]-[1e].

The particle diameter of the abrasive grain shown in the table 1 and 2 is described according to the primary particle diameter of colloidal silica and the order of average secondary granule diameter, and only average secondary granule diameter needles is described fumed silica.As the particle diameter of composite particles, average particulate diameter has been described.

Abbreviation in the table 1 and 2 is meant following compound respectively.

TMAH: Tetramethylammonium hydroxide (the 25% quality aqueous solution)

TEAH: tetraethyl ammonium hydroxide (the 20% quality aqueous solution)

TPAH: TPAOH (the 15% quality aqueous solution)

The ammonium nitrate of mentioning in the table 1 uses with the form of the 20% quality aqueous solution, the KOH that mentions in the table 2 uses with the form of the 10% quality aqueous solution, diethanolamine uses by the form of the quality aqueous solution with 10%, HCl uses under concentration 30% quality, be described to " ammonium nitrate " respectively with these materials, " KOH ", " diethanolamine " and " HCl " also mixes the corresponding combined amount shown in obtaining showing.

Table 1

The high density product of slurry	Season alkylammonium salt		Inorganic salt		Abrasive grain			Other additive
										Kind	Combined amount (wt%)	Kind	Combined amount (wt%)	Kind	Particle diameter (nm)	Combined amount (wt%)	Kind	Combined amount (wt%)
	????1Ad	???TMAH	????6	Volatile salt	????5.5	Colloidal silica	???35，70	????9	Do not have										????-
????1Bd										???TMAH	????3	Volatile salt	????1.6	Colloidal silica	???15，25	????9	Do not have	????-
	????1Cd	???TEAH	????3	Ammonium nitrate	????1.6	Colloidal silica	???35，70	????9	Do not have										????-
????1Dd										???TMAH	????2	Ammonium nitrate	????0.9	Colloidal silica	???35，70	????9	Ammonia	????1
	????1Ed	???TMAH	????3	Volatile salt	????1.4	Fumed silica	???230	????6	Do not have										????-
????1Fd										???TPAH	????0.6	Volatile salt	????0.6	Colloidal silica	???70，150	????1.8	Do not have	????-
	????1Gd	???TEAH	????4.5	Volatile salt	????4	Colloidal silica	???35，70	????4.5	Do not have										????-
????1Hd										???TMAH	????3	Volatile salt	????1.6	Compound silica	???180	????5	Do not have	????-
	????1Id	???TMAH	????6	Ammonium nitrate	????5.5	Colloidal silica	???35，70	????9	Hydroxy ethyl cellulose										????0.05

Table 2

The high density product of slurry	Additive 1		Additive 2		Abrasive grain
								Kind	Combined amount (wt%)	Kind	Combined amount (wt%)	Kind	Particle diameter (nm)	Combined amount (wt%)
	????1ad	??TMAH	??????4	????HCl	?????3	Colloidal silica	????35，70								??????6
????1bd								??TMAH	??????6	Do not have	?????-	Colloidal silica	????15，25	??????6
	????1cd	Diethanolamine	??????5	Do not have	?????-	Fumed silica	????230								??????6
????1dd								??KOH	??????5	Do not have	?????-	Colloidal silica	????70，150	??????9
	????1ed	??KOH	??????5	????HCl	?????3	Colloidal silica	????70，150								??????9

[3] be used for the preparation of the water dispersion of chemically machinery polished:

High density product [1Ad]-[1Id] that will in step [2], prepare and [1ad]-[1ed] after preparation at 25 ℃ down after the placement 2 hours, take out its part, and to wherein adding ion exchanged water, they are diluted to the corresponding dilution rate shown in table 3 and 4, obtain slurry [1A]-[1I] and contrast slurry [1a]-[1e].The content of the respective components of the every kind of slurry that so obtains and pH value provide in table 3 and 4.

, after 40 ℃ store 90 days down, they are diluted according to above-mentioned identical mode at the high density product, obtain slurry [1A]-[1I] and contrast slurry [1a]-[1e].The pH value of the every kind of slurry that so obtains provides in table 3 and 4.

Abbreviation in the table 3 and 4, TMAH, TEAH and TPAH are meant the identical compound in the table 1 and 2.

Table 3

Slurry	Thinning ratio	Season alkylammonium salt		Inorganic salt		Abrasive grain			Other additive		????????????????pH
													Kind	Combined amount (wt%)	Kind	Combined amount (wt%)	Kind	Particle diameter (nm)	Combined amount (wt%)	Kind	Combined amount (wt%)	After preparation 2 hours the time	After preparation 90 days the time
		???1A	???10	???TMAH	????0.6	Volatile salt	???0.55	Colloidal silica	???35，70	????0.9	Do not have	????-												???10.5	???10.3
???1B	???10												???TMAH	????0.3	Volatile salt	???0.16	Colloidal silica	???15，25	????0.9	Do not have	????-	???10.6	???10.4
		???1C	???10	???TEAH	????0.3	Ammonium nitrate	???0.16	Colloidal silica	???35，70	????0.9	Do not have	????-												???10.6	???10.5
???1D	???10												???TMAH	????0.2	Volatile salt	???0.09	Colloidal silica	???35，70	????0.9	Ammonia	????0.1	???11.0	???11.1
		???1E	???10	???TMAH	????0.3	Volatile salt	???0.14	Fumed silica	???230	????0.6	Do not have	????-												???11.0	???11.0
???1F	???2												???TPAH	????0.3	Volatile salt	???0.3	Colloidal silica	???70，150	????0.9	Do not have	????-	???9.2	???9.1
		???1G	???5	???TEAH	????0.9	Volatile salt	???0.8	Colloidal silica	???35，70	????0.9	Do not have	????-												???10.6	???10.4
???1H	???10												???TMAH	????0.3	Volatile salt	???0.16	Compound silica	???180	????0.5	Do not have	????-	???10.6	???10.5
		???1I	???10	???TMAH	????0.6	Ammonium nitrate	???0.55	Colloidal silica	???35，70	????0.9	Hydroxy ethyl cellulose	????0.005												???10.5	???10.3

Table 4

Slurry	Thinning ratio	Additive 1		Additive 2		Abrasive grain			??????????????????pH
											Kind	Combined amount (wt%)	Kind	Combined amount (wt%)	Kind	Particle diameter (nm)	Combined amount (wt%)	After preparation 2 hours the time	After preparation 90 days the time
		???1a	???10	??TMAH	????0.4	???HCl	????0.3	Colloidal silica	???35，70	????0.6										????10.3	????10.1
???1b	???10										??TMAH	????0.6	Do not have	????-	Colloidal silica	???15，25	????0.6	????12.1	????11.5
		???1c	???10	Diethanolamine	????0.5	Do not have	????-	Fumed silica	???230	????0.6										????11.2	????11.3
???1d	???10										??KOH	????0.5	Do not have	????-	Colloidal silica	???70，150	????0.9	????12.2	????11.5
		???1e	???10	??KOH	????0.5	???HCl	????0.3	Colloidal silica	???70，150	????0.9										????10.5	????10.5

[4] assessment of the polishing performance on polysilicon film:

Embodiment 1-1:

(i) assessment of the polishing speed during the polishing polycrystalline silicon film:

The slurry [1A] that use prepares in step [3] (product of dilution after preparing 2 hours), and the 8-inch silicon substrate that will have heat oxide film is placed on chemical mechanical polishing apparatus (model " EPO112 ", make by Ebara company) on, the polishing pad that utilization is made by cellular polyurethane (Rodel Nitta, the product of Ltd.; Trade(brand)name " IC1000 ") polishes the polysilicon film (film thickness: 5,000 dusts) that on base material, forms under the following conditions.The polishing speed result of polysilicon film be 4250 dusts/minute.

Carrier load: 300g/cm ²

Carrier speed of rotation: 50rpm

Worktable speed of rotation: 55rpm

The feed rate of slurry: 200ml/min

Polishing time: 1 minute

[ii] optionally assesses at the polishing and the removal of polysilicon film and silicon oxide film:

The polishing speed of silicon oxide film is determined according to the identical mode of assessment [i], only is to use 8-inch silicon oxide film base material (film thickness: 5,000 dusts) substitute the 8-inch silicon substrate of assessing in [i] with heat oxide film.As a result, the polishing speed of silicon oxide film be 5 dusts/minute.In view of the above, the polishing and the removal selectivity at polysilicon film and silicon oxide film of slurry [1A] can be calculated as 850.

[iii] optionally assesses at the polishing and the removal of polysilicon film and silicon nitride film:

The polishing speed of silicon nitride film is determined according to the identical mode of assessment [i], only is to use 8-inch silicon nitride film base material (film thickness: 1,000 dust) substitute the 8-inch silicon substrate of assessing in [i] with heat oxide film.As a result, polishing speed be 5 dusts/minute.In view of the above, the polishing and the removal selectivity at polysilicon film and silicon nitride film of slurry [1A] can be calculated as 850.

The assessment of [iv] erosive:

Polished finish is carried out according to the same way as of assessment [i], only be to use the deposition of polycrystalline wherein (the silicon single crystal deposition: 3500 dusts) comprise wiring 50 μ m wide/the wide pattern of non-wiring portion 9 μ m and wiring 2 μ m are wide/8-inch silicon substrate with heat oxide film and polishing time that wafer on the silicon oxide film of the wide pattern of non-wiring portion 0.35 μ m substitutes in the assessment [i] set the time of being above standard 30% for.After polishing, measure with erosion utilization step height and surfaceness meter (model " P-10 " is made by KLA-Tencor Co.) on the alternately wiring position with wiring width 2 μ m in alternately wiring position with wiring width 50 μ m.As a result, the erosion on the position of alternately connecting up is respectively 750 dusts and 600 dusts.If these values are not more than 1000 dusts and 700 dusts respectively, corrode patience and can positively say well.

By the way, be above standard the time nearly 30% polishing time in such a way based on the polysilicon film polishing speed calculating of in assessment [i], measuring and carry out.

Polishing time (min)=[polycrystalline deposition (dust)/polysilicon film polishing speed (dust/minute)] * 1.3

(the v) assessment of the stability of the high density product of slurry:

The assessment of respective item is carried out according to identical with assessment (i)-(iv) basically mode, only be to use by substitute the slurry [1A] that diluting high-concentration product [1Ad] obtains 2 hours the time after preparing of pass through in the assessment (i)-(iv) at preparation high density product [1Ad] slurry [1A] that diluting high-concentration product [1Ad] obtains after 40 ℃ store 90 days down afterwards.The results are shown in table 5.Obviously be appreciated that from table 5, the performance of slurry [1A] therein concentration product [1Ad] situation that time dilution in 2 hours is used after preparation and wherein concentration product [1Ad] after preparation, after 40 ℃ store 90 days down, dilute between the situation of use much at one, and so under the high density state, have permanent stability of excellence.

Embodiment 1-2 to 1-7 and Comparative Examples 1-1 to 1-5:

Assessment is carried out according to the identical mode of embodiment 1-1 basically, only is to use the slurry [1A] among its corresponding slurry alternate embodiment 1-1 shown in table 5 and 6.The results are shown in table 5 and 6.

Table 5

Slurry		Embodiment 1-1	Embodiment 1-2	Embodiment 1-3	Embodiment 1-4	Embodiment 1-5	Embodiment 1-6	Embodiment 1-7
											????1A	????1C	????1D	????1F	????1G	????1H	????1I
After preparation, dilute 2 hours the time	The polishing speed of polysilicon film (dust/minute)	????4250	????2600	????3100	????1800	????4450	????2500	????2000
									Polysilicon: the ratio of the polishing speed of silicon oxide	????850	????430	????365	????300	????890	????500	????285
	Polysilicon: the ratio of the polishing speed of silicon nitride	????850	????520	????475	????360	????740	????625	????285
									Corrode (dust) wiring width 50 μ m	????750	????600	????650	????850	????900	????700	????450
	Wiring width 2 μ m	????600	????550	????500	????700	????700	????500	????400
									After preparation, dilute 90 days the time	The polishing speed of polysilicon film (dust/minute)	????4100	????2650	????3150	????1650	????4400	????2600	????2100
Polysilicon: the ratio of the polishing speed of silicon oxide	????820	????405	????395	????330	????735	????520	????300
								Polysilicon: the ratio of the polishing speed of silicon nitride		????970	????530	????450	????365	????735	????650	????280
Corrode (dust) wiring width 50 μ m	????800	????650	????750	????900	????950	????750	????450
								Wiring width 2 μ m		????550	????550	????450	????650	????650	????550	????400

Table 6

Slurry		Comparative Examples 1-1	Comparative Examples 1-2	Comparative Examples 1-3	Comparative Examples 1-4	Comparative Examples 1-5
									????1a	1b	??1c	1d	??1e
After preparation, dilute 2 hours the time	The polishing speed of polysilicon film (dust/minute)	????1300	2850	??200	2300	??1100
							Polysilicon: the ratio of the polishing speed of silicon oxide	????15	30	??less?than?1	10	??10
	Polysilicon: the ratio of the polishing speed of silicon nitride	????90	15	??60	20	??100
							Corrode (dust) wiring width 50 μ m	????1050	1450	??500	1200	??950
	Wiring width 2 μ m	????900	1800	??400	1300	??950
							After preparation, dilute 90 days the time	The polishing speed of polysilicon film (dust/minute)	????1100	1200	??200	1550	??200
Polysilicon: the ratio of the polishing speed of silicon oxide	????10	5	??less?than?1	5	??less?than?1
						Polysilicon: the ratio of the polishing speed of silicon nitride		????80	5	??50	15	??30
Corrode (dust) wiring width 50 μ m	????1000	2050	??550	1650	??1000
						Wiring width 2 μ m		????950	2250	??400	1700	??900

[5] assessment of the polishing performance on the monocrystalline silicon membrane:

Embodiment 1-8:

(the vi) assessment of the polishing speed of monocrystalline silicon membrane:

The slurry [1B] that use prepares in step [3] (product that after preparation, dilutes 2 hours the time), and silicon wafer (E ﹠amp; The product of N Co.) is placed on the chemical mechanical polishing apparatus (model " EP0112 " is made by Ebara company), utilizes polishing pad (Rodel Nitta, the product of Ltd. made by cellular polyurethane; Trade(brand)name " IC1000 ") polishes under the following conditions.The polishing speed result of monocrystalline silicon membrane be 1800 dusts/minute.

Carrier load: 300g/cm ²

Carrier speed of rotation: 50rpm

Worktable speed of rotation: 55rpm

Feed rate slurry: 200ml/min

Polishing time: 3 minutes

(the vii) assessment of the stability of the high density product of slurry:

Basically (identical mode is vi) carried out, and just substitutes and assess (the slurry [1B] that diluting high-concentration product [1Bd] obtains 2 hours the time after preparing of passing through vi) by the slurry [1B] that diluting high-concentration product [1Bd] obtains after 40 ℃ store 90 days down after preparation according to assessment in assessment.

As a result, the polishing speed of monocrystalline silicon membrane be 1750 dusts/minute, and the situation difference of diluting 2 hours the time after preparation with its middle and high concentration product [1Bd] is less.

Embodiment 1-9:

Assessment is carried out according to the same way as of embodiment 1-8 basically, and just slurry [1E] is used for the slurry [1B] of alternate embodiment 1-8.

The result, for the slurry [1E] that after preparation, dilutes 2 hours the time, the polishing speed of monocrystalline silicon membrane be 2200 dusts/minute, simultaneously at preparation high density product [1Ed] slurry [1E] of dilution after 40 ℃ store 90 days down afterwards, the polishing speed of monocrystalline silicon membrane be 2320 dusts/minute and with its middle and high concentration product [1Ed] after preparation 2 hours the time situation of dilution compare and do not have reduction at all.

＜relate to the embodiment of second slurry 〉

[1] comprise the preparation of the water dispersion of the abrasive grain of forming by inorganic particle or composite particles:

(1) comprises the preparation of the water dispersion of inorganic abradant particle (colloidal silica)

To 2-rise the 70g aqueous ammonia of packing in the flask (concentration: 25% quality), 40g ion exchanged water, 175g ethanol and 21g tetraethoxysilane, and mixture is heated to 60 ℃ under 180rpm stirs.Under this temperature, after the continuously stirring 2 hours, its cooling is obtained the alcoholic dispersion of colloidal silica at mixture.Utilize vaporizer simultaneously to add ion exchanged water down and remove alcoholic acid technology and repeat several times, prepare and comprise the water dispersion that 20% quality has the colloidal silica of average primary particle diameter 35nm and average secondary granule diameter 70nm at 80 ℃.

Comprise the water dispersion that 20% quality has the colloidal silica of average primary particle diameter 15nm and average secondary granule diameter 25nm and prepare according to mode same as described above basically in addition, just change the add-on of ethanol and tetraethoxysilane.

(2) comprise the preparation of the water dispersion of the abrasive grain of forming by composite particles:

(a) comprise the preparation of aqueous dispersion of polymer particles:

Rise 90 parts of (following " part ") methyl methacrylate, the 5 parts of methoxy polyethylene glycol methacrylate-styrene polymer (products of Shin-Nakamura chemistry company limited of being called simply of packing in the flask to 2-; Trade(brand)name " NK Ester M-90G; #400 "), 5 parts of 4-vinylpridines, 2 parts of azo-type initiators for polymerization (products of Wako Pure Chemical Industries Ltd., trade(brand)name " V50 ") and 400 parts of ion exchanged waters, and mixture under agitation is being heated to 70 ℃ to carry out polyreaction 6 hours under identical temperature under the nitrogen atmosphere, obtain comprising the aqueous dispersion of polymer particles with average particulate diameter 150nm like this, wherein said polymkeric substance has amino and polyglycol chain.The polyreaction productive rate is 95%.

(b) comprise the preparation of the water dispersion of composite particles:

Comprise aqueous dispersion of polymer particles that 10% quality obtains with 100 parts in above step (a) and add 2-and rises flask, add 1 part of methyltrimethoxy silane in addition, and with the gained mixture 40 ℃ of stirrings 2 hours down.Then, use the pH regulator to 2 of nitric acid, obtain water dispersion (2-a) this mixture.Comprise 10% quality colloidal silica (Nissan ChemicalIndustries, the product of Ltd.; Trade(brand)name " Snowtex O ", average primary particle diameter: the pH of water dispersion 10-20nm) uses potassium hydroxide to be adjusted to 8, obtains water dispersion (2-b).By the way, the ζDian Shi that is included in the poly methyl methacrylate particle in the water dispersion (2-a) is+17mV that the ζDian Shi that is included in the silica granule in the water dispersion (2-b) simultaneously is-40mV.

Add gradually and, the gained mixture was stirred 2 hours in addition at 50 parts of water dispersions (2-b), obtain comprising and have the colloidal silica particulate particulate water dispersion that is keyed on the polymer beads with after 100 parts of water dispersions (2-a) mix 2 hours.In this water dispersion, add 2 parts of vinyltriethoxysilanes, and mixture was stirred 1 hour.Then, add 1 part of tetraethoxysilane, and with mixture heating up to 60 ℃, continuously stirring 3 hours and with postcooling under this temperature obtains comprising the water dispersion of composite particles like this.The average particulate diameter of composite particles is 180nm.Composite particles make adhere to the lip-deep silica granule of polymer beads cover its 80%.

[2] be used for the preparation of high density product of the water dispersion of chemically machinery polished:

(a) preparation of first aqueous dispersion materials (I)

Ion exchanged water so that reaching the amount adding 1-of 100% quality, the total mass of gained high density product is risen polyethylene bottle, with concentration is that the tetramethylammonium hydroxide aqueous solution of 25% quality adds ion exchanged water to obtain concentration 5% quality, in Tetramethylammonium hydroxide content, and mixture fully stirred.Then, the aqueous solution that under agitation adds volatile salt in volatile salt content, adds 9% quality colloidal silica (average primary particle diameter: 35nm to obtain concentration 3% quality simultaneously; Average secondary granule diameter: 70nm).After the gained mixture fully stirs, it is filtered the strainer with hole dimension 5 μ m, obtain the high density product [2Ad] of water dispersion [2A], be first aqueous dispersion materials (I) that constitutes biliquid mixed type slurry.

Corresponding high density product [2Bd]-[2Ed] water dispersion [2B]-[2E] (being first aqueous dispersion materials (I)) is made according to above-mentioned identical mode basically, and just the kind of respective components and combined amount are according to changing shown in the table 7.

Ion exchanged water so that reaching the amount adding 1-of 100% quality, the total mass of gained high density product is risen polyethylene bottle, and with the corresponding adding ion exchanged water of the aqueous solution shown in " additive 1 " row of table 8, obtain the corresponding combined amount shown in " additive 1 " row of table 8, and the gained mixture fully stirred.Then, the aqueous solution shown in " additive 2 " of table 8 row is under agitation added respectively, obtain the corresponding combined amount shown in " additive 2 " row of table 8.Simultaneously, add abrasive grain, the gained mixture fully stirs, and with strainer with hole dimension 5 μ m of they corresponding filtrations, obtains corresponding high density product [2Fd] and [2Gd] of water dispersion [2F] and [2G], is contrast first aqueous dispersion materials (I).

(b) preparation of second aqueous dispersion materials (II):

Ion exchanged water so that reaching the amount adding 1-of 100% quality, the total mass of gained high density product is risen polyethylene bottle, the aqueous solution of hydroxy ethyl cellulose is added ion exchanged water to obtain concentration 0.15% quality, in hydroxy ethyl cellulose content, and mixture fully stirred.Then, the aqueous solution of trolamine and the aqueous solution of Tetramethylammonium hydroxide are under agitation added, obtain concentration 3% quality and 0.1% quality,, and add colloidal silica (average primary particle diameter: 35nm respectively in trolamine content and Tetramethylammonium hydroxide content; Average secondary granule diameter: 70nm) to obtain combined amount 2.5% quality.After the gained mixture fully stirs, it is filtered the strainer with hole dimension 5 μ m, obtain the high density product [2ad] of water dispersion [2a], it is second aqueous dispersion materials (II) that constitutes biliquid mixed type slurry.

Corresponding high density product [2bd]-[2dd] of water dispersion [2b]-[2d] (being second aqueous dispersion materials (II)) makes according to above-mentioned identical mode basically, is that the kind of corresponding 5 components and combined amount are according to changing shown in the table 7.

Be used for the hydroxy ethyl cellulose of water dispersion [2dd] and carboxy methyl cellulose and its aqueous solution be fed to the resin column of the mixture that is filled with H type ion exchange resin and OH type ion exchange resin so that their contact ions exchange resins and purifying by a direction under fixed rate by corresponding.

Ion exchanged water so that reaching the amount adding 1-of 100% quality, the total mass of gained high density product is risen polyethylene bottle, and with the corresponding adding ion exchanged water of the aqueous solution shown in " additive 3 " row of table 8, obtain the corresponding combined amount shown in " additive 3 " row of table 8, and the gained mixture fully stirred.Then, the aqueous solution shown in " additive 4 " of table 8 row is under agitation added respectively, obtain the corresponding combined amount shown in " additive 4 " row of table 8.Simultaneously, add abrasive grain, the gained mixture fully stirs, and with strainer with hole dimension 5 μ m of they corresponding filtrations, obtains corresponding high density product [2ed] and [2fd] of water dispersion [2e] and [2f], is contrast second aqueous dispersion materials (I).By the way, the particle diameter of the abrasive grain shown in the table 7 and 8 is described according to the average primary particle diameter of colloidal silica and the order of average secondary granule diameter.As the particle diameter of composite particles, average particulate diameter has been described.

Abbreviation in the table 7 and 8 is meant following compound respectively.

TMAH: Tetramethylammonium hydroxide (the 25% quality aqueous solution)

TEAH: tetraethyl ammonium hydroxide (the 20% quality aqueous solution)

HEC: hydroxy ethyl cellulose (the 1% quality aqueous solution)

CMC: carboxy methyl cellulose (the 1% quality aqueous solution)

Volatile salt in the table 7 uses with the form of the 20% quality aqueous solution, ammonium nitrate uses with the form of the 20% quality aqueous solution, and trolamine and diethanolamine use with the form of the 20% quality aqueous solution respectively, and the KOH in the table 8 uses with the form of the 10% quality aqueous solution and HCl uses under concentration 30% quality.These materials prepare the corresponding combined amount shown in table 7 and 8.

Table 7

Liquid I	The high density product of water dispersion	Season alkylammonium salt		Inorganic salt		Abrasive grain			Other additive
											Kind	Combined amount (wt%)	Kind	Combined amount (wt%)	Kind	Particle diameter (nm)	Combined amount (wt%)	Kind	Combined amount (wt%)
		?????2Ad	???TMAH	????5.0	Volatile salt	????3.0	Colloidal silica	???35，70	????9.0	Do not have										????-
	?????2Bd										???TMAH	????3.0	Ammonium nitrate	????1.6	Colloidal silica	???15，25	????9.0	Do not have	????-
		?????2Cd	???TEAH	????4.5	Volatile salt	????4.0	Colloidal silica	???35，70	????4.5	Do not have										????-
	?????2Dd										???TMAH	????3.0	Volatile salt	????1.6	Compound silica	???180	????5.0	Do not have	????-
		?????2Ed	???TMAH	????2.0	Volatile salt	????0.9	Colloidal silica	???35，70	????9.0	Ammonia										????1.0
	Liquid II										The high density product of water dispersion	Water-soluble polymers		Alkaline organic compound		Abrasive grain			Other additive
Kind		Combined amount (wt%)	Kind	Combined amount (wt%)	Kind	Particle diameter (nm)	Combined amount (wt%)	Kind	Combined amount (wt%)
										?????2ad		????HEC	????0.15	Trolamine	????3.0	Colloidal silica	???35，70	????2.5	???-	????0.1
?????2bd		????HEC	????0.50	Diethanolamine	????5.0	Colloidal silica	???15，25	????6.0	Do not have		????-
										?????2cd		????HEC	????0.60	Trolamine	????7.0	Compound silica	???180	????6.0	???-	????0.05
?????2dd		????CMC	????0.75	Trolamine	????4.5	Do not have	???-	????-	Do not have		????-

Table 8

Liquid I	The high density product of water dispersion	Additive 1		Additive 2		Abrasive grain
									Kind	Combined amount (wt%)	Kind	Combined amount (wt%)	Kind	Particle diameter (nm)	Combined amount (wt%)
		????2Fd	???TMAH	????4.0	???HCl	????3.0	Colloidal silica	???35，70								????6.0
	????2Gd								???KOH	????5.0	Do not have	????-	Colloidal silica	???35，70	????9.0
		Liquid II	The high density product of water dispersion	Additive 3		Additive 4		Abrasive grain
Kind	Combined amount (wt%)										Kind	Combined amount (wt%)	Kind	Particle diameter (nm)	Combined amount (wt%)
				??????2ed	???HEC	???0.5	???KOH	????0.2	Colloidal silica	???35，70						????2.5
??????2fd	Do not have		???-								Diethanolamine	????5.0	Colloidal silica	???15，25	????6.0

By the way, in table 7 and 8, " liquid I " corresponding first aqueous dispersion materials (I) and second aqueous dispersion materials (II) of being meant with " liquid II ".

[3] be used for the preparation of the water dispersion (biliquid mixes 5 type slurry) of chemically machinery polished:

High density product [2Ad]-[1Gd] that will in step [2], prepare and [2ad]-[2fd] after preparation at 25 ℃ down after the placement 2 hours, take out its part, and to wherein adding ion exchanged water, they are diluted to the corresponding dilution rate shown in table 9 and 10, obtain slurry [2A]-[2G] and contrast slurry [2a]-[2f].The content of the respective components of the slurry that so obtains and pH value provide in table 9 and 10.

With above corresponding high density product after 40 ℃ down store 90 days, they are diluted according to above-mentioned identical mode obtain slurry [2A]-[2G] and contrast slurry [2a]-[2f].The pH value of the slurry that so obtains provides in table 9 and 10.

Abbreviation in the table 9 and 10, TMAH, TEAH, HEC and CMC are meant the identical compound in the table 7 and 8.

Table 9

Liquid I	Slurry	Thinning ratio	Season alkylammonium salt		Inorganic salt		Abrasive grain			Other additive		?????????????pH
														Kind	Combined amount (wt%)	Kind	Combined amount (wt%)	Kind	Particle diameter (nm)	Combined amount (wt%)	Kind	Combined amount (wt%)	After preparation 2 hours the time hour	After preparation 90 days the time hour
			???2A	???10	???TMAH	????0.5	Volatile salt	????0.3	Colloidal silica	???35，70	????0.9	Do not have	?????-												????10.8	???10.8
	???2B	???10												???TMAH	????0.3	Ammonium nitrate	????0.16	Colloidal silica	???15，25	????0.9	Do not have	?????-	????10.6	???10.5
			???2C	???5	???TEAH	????0.9	Volatile salt	????0.8	Colloidal silica	???35，70	????0.9	Do not have	?????-												????10.6	???10.4
	???2D	???10												???TMAH	????0.3	Volatile salt	????0.16	Compound silica	???180	????0.5	Do not have	?????-	????10.6	???10.5
			???2E	???10	???TMAH	????0.2	Volatile salt	????0.09	Colloidal silica	???35，70	????0.9	Ammonia	?????0.1												????11.0	???11.1
	Liquid II	Slurry												Thinning ratio	Water-soluble polymers		Alkaline organic compound		Abrasive grain			Other additive		?????????????pH
Kind			Combined amount (wt%)	Kind	Combined amount (wt%)	Kind	Particle diameter (nm)	Combined amount (wt%)	Kind	Combined amount (wt%)	After preparation 2 hours the time hour	After preparation 90 days the time hour
													???2a		????5	????HEC	???0.03	Triethanol ammonium	????0.6	Colloidal silica	????35，70	????0.5	???-	????0.02	???10.1	???10.1
???2b		????5	????HEC	???0.1	The di-alcohol ammonium	????1.0	Colloidal silica	????15，25	????1.2	Do not have	????-	???10.3		???10.2
													???2c		????10	????HEC	???0.06	Triethanol ammonium	????0.7	Compound silica	????180	????0.6	???-	????0.005	???10.2	???10.2
???2d		????5	????CMC	???0.15	Triethanol ammonium	????0.9	Do not have	????-	????-	Do not have	????-	???10.6		???10.5

Table 10

Liquid I	Slurry	Thinning ratio	??????????1		???????????2		Abrasive grain			??????????pH
												Kind	Combined amount (wt%)	Kind	Combined amount (wt%)	Kind	Particle diameter (nm)	Combined amount (wt%)	After preparation 2 hours the time hour	After preparation 90 days the time hour
			???2F	???10	???TMAH	????0.4	???HEC	????0.3	Colloidal silica	???35，70	????0.6										???10.3	???10.1
	???2G	???10										???KOH	????0.5	Do not have	????-	Colloidal silica	???35，70	????0.9	???12.2	???11.5
			Liquid II	Slurry	Thinning ratio	Additive 3		Additive 4		Abrasive grain											??????????pH
Kind	Combined amount (wt%)	Kind											Combined amount (wt%)	Kind	Particle diameter (nm)	Combined amount (wt%)	After preparation 2 hours the time hour	After preparation 90 days the time hour
						???2e	???5	???HEC	????0.1	??KOH	????0.04	Colloidal silica							???35，70	????0.5	???10.3	???10.1
???2f	???10	Do not have		????-	Triethanol ammonium								????0.5	Colloidal silica	???15，25	????0.6	???11.2	???11.0

By the way, in table 9 and 10, " liquid I " corresponding first aqueous dispersion materials (I) and second aqueous dispersion materials (II) of being meant with " liquid II ".

[4] assessment of the polishing performance on the polysilicon film:

Embodiment 2-1:

(i) assessment of the polishing speed on the polysilicon film:

Water dispersion [2A] that use prepares in step [3] (product of dilution after preparing 2 hours) and water dispersion [2a] (product of dilution after preparing 2 hours) polish the polysilicon film (film thickness: 5,000 dusts) on the 8-inch silicon substrate with heat oxide film.Be placed on the chemical mechanical polishing apparatus (model " EPO112 " is made by Ebara company) polishing pad (Rodel Nitta, the product of Ltd. that utilization is made by cellular polyurethane particularly, and with silicon substrate; Trade(brand)name " IC1000 ") polishes this polysilicon film under the following conditions.Corresponding water dispersion is fed to worktable by independent pipeline.The polishing speed result of polysilicon film be 2500 dusts/minute.

Carrier load: 300g/cm ²

Carrier speed of rotation: 50rpm

Worktable speed of rotation: 55rpm

The feed rate of slurry: 125ml/min

Polishing time: 1 minute.

[ii] optionally assesses at the polishing and the removal of polysilicon film and silicon oxide film:

The polishing speed of silicon oxide film determines that according to the identical mode of assessment [i] (film thickness: 5,000 dusts) 8-inch silicon substrate with heat oxide film and the polishing time that substitutes in the assessment [i] changed into 3 minutes only to be to use 8-inch silicon oxide film base material.As a result, polishing speed be 6 dusts/minute.In view of the above, the biliquid mixed type slurry of forming by the mixture of water dispersion [2A] and water dispersion [2a] at the polishing of polysilicon film and silicon oxide film and remove selectivity and can be calculated as 415.

[iii] optionally assesses at the polishing and the removal of polysilicon film and silicon nitride film:

The polishing speed of silicon nitride film determines that according to the identical mode of assessment [i] (film thickness: 1,000 dust) 8-inch silicon substrate with heat oxide film and the polishing time that substitutes in the assessment [i] changed into 3 minutes only to be to use 8-inch silicon nitride film base material.As a result, polishing speed be 5 dusts/minute.In view of the above, the biliquid mixed type slurry of forming by the mixture of water dispersion [2A] and water dispersion [2a] at the polishing of polysilicon film and silicon nitride film and remove selectivity and can be calculated as 500.

The assessment of [iv] erosive:

Polished finish is carried out according to the same way as of assessment [i], only be to use the deposition of polycrystalline wherein (the silicon single crystal deposition: 3500 dusts) comprise wiring 50 μ m wide/the wide pattern of non-wiring portion 9 μ m and wiring 2 μ m are wide/8-inch silicon substrate with heat oxide film and polishing time that wafer on the silicon oxide film of the wide pattern of non-wiring portion 0.35 μ m substitutes in the assessment [i] set the time of being above standard 30% for.After polishing, measure with erosion utilization step height and surfaceness meter (model " P-10 " is made by KLA-Tencor Co.) on the alternately wiring position with wiring width 2 μ m in alternately wiring position with wiring width 50 μ m.As a result, the erosion on the position of alternately connecting up is respectively 510 dusts and 440 dusts.If these values are not more than 600 dusts and 500 dusts respectively, corrode patience and can positively say well.

By the way, be above standard the time nearly 30% polishing time in such a way based on the polysilicon film polishing speed calculating of in assessment [i], measuring and carry out.

Polishing time (min)=[polycrystalline deposition (dust)/polysilicon film polishing speed (dust/minute)] * 1.3

(the v) assessment of scratch:

For the polysilicon film after polishing in the assessment (i), the sum that appears at the whole lip-deep scratch of each glazed surface utilizes wafer defect detecting device (model " KLA2351 " is made by KLA-Tencor Co.) to count.As a result, number goes out a scratch.

(the vi) assessment of the stability of the high density product of water dispersion:

To the assessment of respective item according to basically with assessment (i)-(v) identical mode is carried out, only be to use by the biliquid mixed type slurry that diluting high-concentration product [2Ad] and [2ad] obtain after 40 ℃ store 90 days down after preparation substitute assess (i)-(passing through v) preparing after diluting high-concentration product [2Ad] and [2ad] biliquid mixed type slurry 2 hours the time.The results are shown in table 11.

Obviously be appreciated that from table 11, the performance of water dispersion [2A] and water dispersion [2a] therein concentration product [2Ad] and [2ad] situation that dilution is used 2 hours the time after preparation and wherein concentration product [2Ad] and [2ad] after preparation, after 40 ℃ store 90 days down, dilute between situation of use much at one, and so under the high density state, have permanent stability of excellence.

Embodiment 2-2 to 2-7 and Comparative Examples 2-1 to 2-5:

Assessment is carried out according to the identical mode of embodiment 2-1 basically, only is to use water dispersion [2A] and [2a] among its corresponding first aqueous dispersion materials (I) shown in table 11 and 12 and second aqueous dispersion materials (II) the alternate embodiment 2-1.The results are shown in table 11 and 12.

Table 11

		Embodiment 2-1	Embodiment 2-2	Embodiment 2-3	Embodiment 2-4	Embodiment 2-5	Embodiment 2-6	Embodiment 2-7
									First aqueous dispersion materials (I)		2A	2A	????2B	2C	??2A	??2D	????2E
First aqueous dispersion materials (II)		2a	2a	????2b	2d	??2d	??2c	????2d
									Blending means (I: II)		On platform, mix	On platform, mix	Mix by supply line	Mix by supply line	On platform, mix	Mix by supply line	Mix by supply line
Ratio (the I: II) of the feed rate of slurry		125∶125	75∶175	????125∶125	175∶75	??150∶150	??175∶100	????125∶125
									After preparation, dilute 2 hours the time	The polishing speed of polysilicon film (dust/minute)	2500	1750	????1200	2950	??1900	??2300	????2200
Polysilicon: the ratio of the polishing speed of silicon oxide	415	350	????240	420	??270	??460	????440
								Polysilicon: the ratio of the polishing speed of silicon nitride		500	435	????300	490	??380	??575	????550
Corrode (dust) wiring width 50 μ m	510	350	????350	550	??500	??500	????400
								Wiring width 2 μ m		440	300	????300	500	??400	??350	????350
Scratch (number/wafer)	1	0	????1	2	??0	??1	????0
								After preparation, dilute 90 days the time		The polishing speed of polysilicon film (dust/minute)	2450	1600	????1150	2800	??1950	??2400	????2250
Polysilicon: the ratio of the polishing speed of silicon oxide	410	320	????290	400	??280	??400	????450
									Polysilicon: the ratio of the polishing speed of silicon nitride	490	400	????290	560	??325	??600	????560
Corrode (dust) wiring width 50 μ m	450	350	????300	600	??600	??450	????400
									Wiring width 2 μ m	400	350	????300	450	??450	??400	????350
Scratch (number/wafer)	1	0	????0	3	??1	??0	????0

Table 12

		Comparative example 2-1	Comparative example 2-2	Comparative example 2-3	Comparative example 2-4	Comparative example 2-5
							First aqueous dispersion materials (I)		??2A	??-	????2F	??2G	????2A
First aqueous dispersion materials (II)		??-	??2a	????2e	??2f	????2e
							Blending means (I: II)		On platform, mix	On platform, mix	Mix by supply line	Mix by supply line	On platform, mix
Ratio (the I: II) of the feed rate of slurry		??200∶-	??-∶200	????125∶125	??175∶75	????75∶175
							After preparation, dilute 2 hours the time	The polishing speed of polysilicon film (dust/minute)	??4250	??450	????1100	??3300	????1800
Polysilicon: the ratio of the polishing speed of silicon oxide	??850	??150	????15	??660	????35
						Polysilicon: the ratio of the polishing speed of silicon nitride		??850	??225	????90	??825	????180
Corrode (dust) wiring width 50 μ m	??750	??350	????1000	??900	????800
						Wiring width 2 μ m		??600	??300	????900	??800	????700
Scratch (number/wafer)	??30	??0	????1	??50	????15
						After preparation, dilute 90 days the time		The polishing speed of polysilicon film (dust/minute)	??4100	??550	????1200	??3100	????1850
Polysilicon: the ratio of the polishing speed of silicon oxide	??820	??180	????15	??620	????35
							Polysilicon: the ratio of the polishing speed of silicon nitride	??910	??275	????85	??775	????185
Corrode (dust) wiring width 50 μ m	??800	??350	????1050	??950	????850
							Wiring width 2 μ m	??400	??300	????950	??800	????700
Scratch (number/wafer)	??45	??0	????0	??45	????10

[5] assessment of the polishing performance on the monocrystalline silicon membrane:

Embodiment 2-8:

(vii) assess the polishing speed monocrystalline silicon membrane:

The water dispersion [2A] that use prepares in step [3] and [2a] (product that after preparation, dilutes 2 hours the time), and with silicon wafer (E ﹠amp; The product of M Co.) is placed on the chemical mechanical polishing apparatus (model " EPO112 " is made by Ebara company), polishes according to step [4] same way as (i).

The polishing speed of monocrystalline silicon membrane be 1400 dusts/minute.

(the viii) assessment of scratch:

(polysilicon film after polishing vii), (same way as number v) goes out the scratch number according to assessment for assessment.As a result, number does not go out scratch.

(ix) assessment of the stability of the high density product of water dispersion:

Basically (identical mode is vii) carried out, and only is to use and substitutes by the biliquid mixed type slurry that diluting high-concentration product [2Ad] and [2ad] obtain after 40 ℃ down store 90 days after preparation and to assess (the biliquid mixed type slurry that diluting high-concentration product [2Ad] and [2ad] obtains 2 hours the time after preparing of passing through vii) according to assessment in assessment.

The result, the polishing speed of monocrystalline silicon membrane be 1300 dusts/minute, number does not go out scratch, even and use by after preparation at 40 ℃ of storage 90 days biliquid mixed type slurry of obtaining of diluting high-concentration product [2Ad] and [2ad] afterwards down, the difference of polishing performance is less.

[effect of the present invention]

The first aqueous dispersion for chemically mechanical polishing according to the present invention has excellent surface plane ability, therefore, polished surface less appearance in planarization steps is recessed curved by chemically mechanical polishing, corrode or similar phenomenon, and have a high storage stability, therefore prevent even rotten and therefore have excellent long-time stability along with the time when under the high concentration state, storing.

The first CMP process according to the present invention is realized high polishing speed when polishing silicon fiml such as polysilicon film, and has in polishing and excellence selective and excellence selective in polishing and when removing polysilicon film and nitride film when removing polysilicon film and silicon oxide film.

The second aqueous dispersion for chemically mechanical polishing according to the present invention has excellent surface plane ability, therefore, polished surface less appearance in planarization steps is recessed curved by chemically mechanical polishing, corrode or similar phenomenon, do not cause or reduce at least the blemish comprise scratch, therefore have high storage stability, prevent even rotten and therefore have excellent long-time stability along with the time when under the high concentration state, storing.

At the second aqueous dispersion for chemically mechanical polishing according to the present invention, if soluble quaternary ammonium is the compound that is expressed as structural formula (1), polishing speed further improves.

If inorganic acid salt is inorganic ammonium salt, can fully prevent recessed curved and erosion.

If it is used for polished silicon type film, polishing speed is high, and prevents recessed curved and similar phenomenon.

According to the second CMP process of the present invention, the polished surface of wanting can polish under the not enough speed, recessed curved, corrode and similar phenomenon can reduce, and scratch also can be prevented.

If the ratio of polysilicon film polishing speed and silicon oxide film polishing speed is at least 30, if polishing is carried out under identical condition, what these films can be enough selectively polishes.

If the ratio of polysilicon film polishing speed and silicon oxide film polishing speed is at least 50, if polishing is carried out under identical condition, these films and layer can enough selectivity polish.

According to semiconductor devices production technique of the present invention, can provide to have excellent ganoid and high-quality semiconductor devices.

Claims (23)

1. one kind by with soluble quaternary ammonium, and inorganic acid salt and abrasive grain are sneaked into water medium and the water dispersion that is used for chemically machinery polished that obtains.

2. according to the water dispersion that is used for chemically machinery polished of claim 1, soluble quaternary ammonium wherein, the content ratio of inorganic acid salt and abrasive grain is respectively the 0.005-5% quality, 0.005-5% quality and 0.01-10% quality.

3. according to the water dispersion that is used for chemically machinery polished of claim 1, further comprise water-soluble polymers.

4. according to the water dispersion that is used for chemically machinery polished of claim 1, wherein soluble quaternary ammonium is the compound that is expressed as following structural formula (1)

[NR ₄] ⁺[OH] ^-????????(1)

Wherein R is the alkyl with 1-4 carbon atom.

5. according to the water dispersion that is used for chemically machinery polished of claim 1, wherein inorganic acid salt is an inorganic ammonium salt.

6. according to the water dispersion that is used for chemically machinery polished of claim 1, it is used for polished silicon type film.

7. a CMP (Chemical Mechanical Polishing) process comprises the water dispersion polishing polished surface of using according to claim 1 of wanting that is used for chemically machinery polished.

8. according to the CMP (Chemical Mechanical Polishing) process of claim 7, silicon oxide film and polysilicon film are at least 30 under the situation of polishing under the identical condition therein wherein to be expressed as the first specific removal rate ratios that polysilicon film removes speed and the ratio of silicon oxide film removal speed.

9. according to the CMP (Chemical Mechanical Polishing) process of claim 7, nitride film and polysilicon film are at least 50 under the situation of polishing under the identical condition therein wherein to be expressed as the second specific removal rate ratios that polysilicon film removes speed and the ratio of nitride film removal speed.

10. one kind is used for the production process for semiconductor devices, and wherein semiconductor devices is made by the polished surface of wanting on the semiconductor substrate being used the water dispersion that is used for chemically machinery polished according to claim 1 polish.

11. one kind by with at least a soluble quaternary ammonium, another alkaline organic compound of water-insoluble quaternary ammonium salt, inorganic acid salt, water-soluble polymers and abrasive grain are sneaked into water medium and the water dispersion that is used for chemically machinery polished that obtains.

12. the water dispersion that is used for chemically machinery polished according to claim 11, soluble quaternary ammonium wherein, another alkaline organic compound of water-insoluble quaternary ammonium salt, inorganic acid salt, the content ratio of water-soluble polymers and abrasive grain is respectively the 0.005-10% quality, 0.005-10% quality, 0.005-8% quality, 0.001-5% quality and 0.01-10% quality.

13. according to the water dispersion that is used for chemically machinery polished of claim 11, wherein soluble quaternary ammonium is the compound that is expressed as following structural formula (1)

[NR ₄] ⁺[OH] ^-????????(1)

Wherein R is the alkyl with 1-4 carbon atom.

14. according to the water dispersion that is used for chemically machinery polished of claim 11, wherein inorganic acid salt is an inorganic ammonium salt.

15. according to the water dispersion that is used for chemically machinery polished of claim 11, it is used for polished silicon type film.

16. a CMP (Chemical Mechanical Polishing) process comprises and uses the water dispersion that is used for chemically machinery polished according to claim 11 to polish want polished surface.

17. according to the CMP (Chemical Mechanical Polishing) process of claim 16, silicon oxide film and polysilicon film are at least 30 under the situation of polishing under the identical condition therein wherein to be expressed as the first specific removal rate ratios that polysilicon film removes speed and the ratio of silicon oxide film removal speed.

18. according to the CMP (Chemical Mechanical Polishing) process of claim 16, nitride film and polysilicon film are at least 50 under the situation of polishing under the identical condition therein wherein to be expressed as the second specific removal rate ratios that polysilicon film removes speed and the ratio of nitride film removal speed.

19. one kind is used for the production process for semiconductor devices, wherein semiconductor devices is made by the polished surface of wanting on the semiconductor substrate being used the water dispersion that is used for chemically machinery polished according to claim 11 polish.

20. material that is used to prepare the water dispersion that is used for chemically machinery polished, comprise by at least a soluble quaternary ammonium and inorganic acid salt are sneaked into first aqueous dispersion materials (I) that water medium obtains, with by another alkaline organic compound of at least a water-soluble polymers and water-insoluble quaternary ammonium salt being sneaked into second aqueous dispersion materials (II) that water medium obtains, wherein abrasive grain is sneaked at least a in first aqueous dispersion materials (I) and second aqueous dispersion materials (II), and the water dispersion that is used for chemically machinery polished prepares by first aqueous dispersion materials (I) and second aqueous dispersion materials (II).

21. according to the material that is used to prepare the water dispersion that is used for chemically machinery polished of claim 20, wherein soluble quaternary ammonium is the compound that is expressed as following structural formula (1)

[NR ₄] ⁺[OH] ^-????????(1)

Wherein R is the alkyl with 1-4 carbon atom.

22. according to the material that is used to prepare the water dispersion that is used for chemically machinery polished of claim 20, wherein first aqueous dispersion materials (I) is 30/70-70/30 with the ratio [(I)/(II)] of second aqueous dispersion materials (II), in quality ratio.

23. according to the material that is used to prepare the water dispersion that is used for chemically machinery polished of claim 20, wherein inorganic acid salt is an inorganic ammonium salt.